Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices

ABSTRACT

The present invention relates to electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films and processes for making such solid films and devices. The electrochromic polymeric solid films of the present invention exhibit beneficial properties and characteristics, especially when compared to known electrochromic media. The electrochromic polymeric solid films are transformed in situ from a low viscosity electrochromic monomer composition by exposure to electromagnetic radiation, and in so doing minimum shrinkage occurs. The electrochromic polymeric solid films of the present invention also perform well under prolonged coloration, outdoor weathering and all-climate exposure, and provide an inherent safety aspect not known to electrochromic media heretofore.

RELATED UNITED STATES PATENT APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.08/406,663, filed Mar. 20, 1995, now abandoned, which is a continuationof U.S. patent application Ser. No. 08/193,557, filed Feb. 8, 1994, nowabandoned, which is a continuation-in-part of U.S. patent applicationSer. No. 08/023,675, filed Feb. 26, 1993 (now abandoned).

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

The present invention relates to reversibly variable electrochromicdevices for varying the transmittance to light, such as electrochromicrearview mirrors, windows and sun roofs for motor vehicles, reversiblyvariable electrochromic elements therefor and processes for making suchdevices and elements.

2. Brief Description of the Related Technology

Reversibly variable electrochromic devices are known in the art. In suchdevices, the intensity of light (e.g., visible, infrared, ultraviolet orother distinct or overlapping electromagnetic radiation) is modulated bypassing the light through an electrochromic medium. The electrochromicmedium is disposed between two conductive electrodes, at least one ofwhich is typically transparent, which causes the medium to undergoreversible electrochemical reactions when potential differences areapplied across the two electrodes. Some examples of these prior artdevices are described in U.S. Pat. Nos. 3,280,701 (Donnelly); 3,451,741(Manos); 3,806,229 (Schoot); 4,712,879 (Lynam) ("Lynam I); 4,902,108(Byker) ("Byker I"); and I. F. Chang, "Electrochromic andElectrochemichromic Materials and Phenomena", in NonemissiveElectrooptic Displays, 155-96, A. R. Kmetz and F. K. von Willisen, eds.,Plenum Press, New York (1976).

Reversibly variable electrochromic media include those wherein theelectrochemical reaction takes place in a solid film or occurs entirelyin a liquid solution. See e.g., Chang.

Numerous devices using an electrochromic medium, wherein theelectrochemical reaction takes place entirely in a solution, are knownin the art. Some examples are described in U.S. Pat. Nos. 3,453,038(Kissa); 5,128,799 (Byker) ("Byker II"); Donnelly; Manos; Schoot; BykerI; and commonly assigned U.S. Pat. Nos. 5,073,012 (Lynam) ("Lynam II");5,115,346 (Lynam) ("Lynam III"); 5,140,455 (Varaprasad) ("VaraprasadI"); 5,142,407 (Varaprasad) ("Varaprasad II"); 5,151,816 (Varaprasad)("Varaprasad III") and 5,239,405 (Varaprasad) ("Varaprasad IV"); andcommonly assigned co-pending U.S. patent application Ser. No. 07/935,784(filed Aug. 27, 1992)]. Typically, these electrochromic devices,sometimes referred to as electrochemichromic devices, aresingle-compartment, self-erasing, solution-phase electrochromic devices.See e.g., Manos, Byker I and Byker II.

In single-compartment, self-erasing, solution-phase electrochromicdevices, the intensity of the electromagnetic radiation is modulated bypassing through a solution held in a compartment. The solution oftenincludes a solvent, at least one anodic compound and at least onecathodic compound. During operation of such devices, the solution isfluid, although it may be gelled or made highly viscous with athickening agent, and the solution components, including the anodiccompounds and cathodic compounds, do not precipitate. See e.g., Byker Iand Byker II.

Certain of these electrochemichromic devices have presented drawbacks.First, a susceptibility exists for distinct bands of color to formadjacent the bus bars after having retained a colored state over aprolonged period of time. This undesirable event is known assegregation. Second, processing and manufacturing limitations arepresented with electrochemichromic devices containingelectrochemichromic solutions. For instance, in the case ofelectrochemichromic devices which contain an electrochemichromicsolution within a compartment or cavity thereof, the size and shape ofthe electrochemichromic device is limited by the bulges andnon-uniformities which often form in such large area electrochemichromicdevices because of the hydrostatic nature of the liquid solution. Third,from a safety standpoint, in the event an electrochemichromic deviceshould break or become damaged through fracture or rupture, it isimportant for the device to maintain its integrity so that, if thesubstrates of the device are shattered, an electrochemichromic solutiondoes not escape therefrom and that shards of glass and the like areretained and do not scatter about. In the known electrochromic devices,measures to reduce breakage or broken glass scattering include the useof tempered glass and/or a laminate assembly comprising at least twopanels affixed to one another by an adhesive. Such measures control thescattering of glass shards in the event of breakage or damage due, forinstance, to the impact caused by an accident.

Numerous devices using an electrochromic medium, wherein theelectrochemical reaction takes place in a solid layer, are known in theart. Typically, these devices employ electrochromic solid-state thinfilm technology [see e.g., N. R. Lynam, "Electrochromic AutomotiveDay/Night Mirrors", SAE Technical Paper Series, 870636 (1987); N. R.Lynam, "Smart Windows for Automobiles", SAE Technical Paper Series,900419 (1990); N. R. Lynam and A. Agrawal, "Automotive Applications ofChromogenic Materials", Large Area Chromogenics: Materials & Devices forTransmittance Control, C. M. Lampert and C. G. Granquist, eds., OpticalEng'g Press, Washington (1990); C. M. Lampert, "Electrochromic Devicesand Devices for Energy Efficient Windows", Solar Energy Materials, 11,1-27 (1984); U.S. Pat. Nos. 3,521,941 (Deb); 4,174,152 (Giglia); Re.30,835 (Giglia); 4,338,000 (Kamimori); 4,652,090 (Uchikawa); 4,671,619(Kamimori); Lynam I; and commonly assigned U.S. Pat. Nos. 5,066,112(Lynam) ("Lynam IV") and 5,076,674 (Lynam) ("Lynam V")].

In solid-state thin film electrochromic devices, an anodicelectrochromic layer and a cathodic electrochromic layer, each layerusually made from inorganic metal oxides, are typically separate anddistinct from one another and assembled in a spaced-apart relationship.The solid-state thin films are often formed using techniques such aschemical vapor deposition or physical vapor deposition. Such techniquesare not attractive economically, however, as they involve cost. Inanother type of solid-state thin film electrochromic device, twosubstrates are coated separately with compositions of photo- orthermo-setting monomers or oligomers to form on one of the substrates anelectrochromic layer, with the electrochromic material present withinthe layer being predominantly an inorganic material, and on the othersubstrate a redox layer. [See Japanese Patent Document JP 63-262,6241.

Attempts have been made to prepare electrochromic media from polymers.For example, it has been reported that electrochromic polymer layers maybe prepared by dissolving in a solvent organic polymers, which containno functionality capable of further polymerization, together with anelectrochromic compound, and thereafter casting or coating the resultingsolution onto an electrode. It has been reported further thatelectrochromic polymer layers are created upon evaporation of thesolvent by pressure reduction and/or temperature elevation. [See e.g.,U.S. Pat. Nos. 3,652,149 (Rogers), 3,774,988 (Rogers) and 3,873,185(Rogers); 4,550,982 (Hirai); Japanese Patent Document JP 52-10,745; andY. Hirai and C. Tani, "Electrochromism for Organic Materials inPolymeric All-Solid State Systems", Appl. Phys. Lett., 43(7), 704-05(1983)]. Use of such polymer solution casting systems has disadvantages,however, including the need to evaporate the solvent prior to assemblingdevices to form polymer electrochromic layers. This additionalprocessing step adds to the cost of manufacture through increasedcapital expenditures and energy requirements, involves potentialexposure to hazardous chemical vapors and constrains the type of deviceto be manufactured.

A thermally cured polymer gel film containing a single organicelectrochromic compound has also been reported for use in displaydevices. [See H. Tsutsumi et al., "Polymer Gel Films with Simple OrganicElectrochromics for Single-Film Electrochromic Devices", J. Polym. Sci.,30, 1725-29 (1992) and H. Tsutsumi et al., "Single Polymer Gel FilmElectrochromic Device", Electrochemica Acta, 37, 369-70 (1992)]. The gelfilm reported therein was said to possess a solvent-like environmentaround the electrochromic compounds of that film. This gel film wasreported to turn brown, and ceased to perform color-bleach cycles, afteronly 35,200 color-bleach cycles.

SUMMARY OF THE INVENTION

The present invention provides electrochromic polymeric solid films("polychromic solid films") that are prepared by an in situ curingprocess different from processes used to prepare the electrochromicpolymer layers known to date, and employ different combinations ofelectrochromic compounds than those that have been placed heretofore insolid electrochromic media. The resulting polychromic solid filmspossess beneficial properties and characteristics, and offer superiorresults, compared to the known electrochromic media. For instance,polychromic solid films overcome well-known manufacturing and useconcerns such as hydrostatic pressure that is particularly troublesomein large area vertically mounted panels, such as windows, or large areamirrors, such as Class 8 truck mirrors. Thus, polychromic solid filmsare extremely well-suited to commercial applications, like themanufacture and use of electrochromic devices. Such electrochromicdevices include, but are not limited to, electrochromic mirrors--e.g.,vehicular, for instance, truck mirrors, particularly large area truckmirrors, automotive interior and exterior mirrors, architectural orspecialty mirrors, like those useful in periscopic or dental and medicalapplications; electrochromic glazings--e.g., architectural, such asthose useful in the home, office or other edifice, aeronautical, such asthose useful in aircraft, or vehicular glazings, for instance, windows,such as windshields, side windows and backlights, sun roofs, sun visorsor shade bands and optically attenuating contrast filters, such ascontrast enhancement filters, suitable for use in connection withcathode ray tube monitors and the like; electrochromic privacy orsecurity partitions; electrochromic solar panels, such as sky lights;electrochromic information displays; electrochromic lenses and eyeglass. Moreover, in view of the teaching herein, any of suchelectrochromic devices may be manufactured to be segmented so that aportion of the device colors preferentially to change the lighttransmittance thereof.

The present invention also provides novel electrochromic monomercompositions comprising anodic electrochromic compounds, cathodicelectrochromic compounds, a monomer component and a plasticizer that areuseful in the formation of such polychromic solid films. Morespecifically, each of the electrochromic compounds are organic ororganometallic compounds. Electrochromic monomer compositions may alsoinclude, but are not limited to, either individually or in combination,cross-linking agents, photoinitiators, photosensitizers, ultravioletstabilizing agents, electrolytic materials, coloring agents, spacers,anti-oxidizing agents, flame retarding agents, heat stabilizing agents,compatibilizing agents, adhesion promoting agents, coupling agents,humectants and lubricating agents.

The present invention further provides novel processes for makingpolychromic solid films by transforming such novel electrochromicmonomer compositions into polychromic solid films through exposure toelectromagnetic radiation for a time sufficient to effect an in situcure.

The present invention still further provides electrochromic devices,such as those referred to above, particularly rearview mirrors, windowsand sun roofs for automobiles, which devices are stable to outdoorweathering, particularly weathering observed due to prolonged exposureto ultraviolet radiation from the sun, and are safety protected againstimpact from an accident. Such outdoor weathering and safety benefits areachieved by manufacturing these devices using as a medium of varyingtransmittance to light the polychromic solid films prepared by the insitu cure of an electrochromic monomer composition containing a monomercomponent that is capable of further polymerization.

The present invention provides for the first time, among other things(1) polychromic solid films that may be transformed from electrochromicmonomer compositions by an in situ curing process through exposure toelectromagnetic radiation, such as ultraviolet radiation; (2) atransformation during the in situ curing process from the low viscosity,typically liquid, electrochromic monomer compositions to polychromicsolid films that occurs with minimum shrinkage and with good adhesion tothe contacting surfaces; (3) polychromic solid films that (a) may bemanufactured to be self-supporting and subsequently laminated betweenconductive substrates, (b) perform well under prolonged coloration, (c)demonstrate a resistance to degradation caused by environmentalconditions, such as outdoor weathering and all-climate exposure,particularly demonstrating ultraviolet stability when exposed to thesun, and (d) demonstrate a broad spectrum of color under an appliedpotential; (4) polychromic solid films that may be manufacturedeconomically and are amenable to commercial processing; (5) polychromicsolid films that provide inherent safety protection not known toelectrochromic media heretofore; and (6) electrochromic monomercompositions that comprise anodic electrochromic compounds and cathodicelectrochromic compounds, which compounds are organic or organometallic.

The self-supporting nature of polychromic solid films provides manybenefits to the electrochromic devices manufactured therewith, includingthe elimination of a compartmentalization means, such as a sealingmeans, since no such means is required to confine or contain apolychromic solid film within an electrochromic device. That polychromicsolid films may be manufactured to be self-supporting also enhancesprocessibility, and vitiates obstacles well-recognized in themanufacturing of electrochromic devices containing known electrochromicmedia, especially those that are to be vertically mounted in theirintended use.

Moreover, since the electrochromic compounds are not free to migratewithin polychromic solid films, in contrast to electrochromic compoundspresent within a liquid solution-phase environment, polychromic solidfilms do not pose the segregation concern as do solution-phaseelectrochemichromic devices; rather, polychromic solid films performwell under prolonged coloration.

Further, from a safety perspective, in the event that electrochromicdevices manufactured with polychromic solid films should break or becomedamaged due to the impact from an accident, no liquid is present to seeptherefrom since the polychromic solid films of the present invention areindeed solid. Also, the need to manufacture electrochromic devices withtempered glass, or with at least one of the substrates being of alaminate assembly, to reduce potential lacerative injuries is obviatedsince polychromic solid films, positioned between, and in abuttingrelationship with, the conductive surface of the two substrates, exhibitgood adhesion to the contacting surfaces. Thus, polychromic solid filmsshould retain any glass shards that may be created and prevent them fromscattering. Therefore, a safety protection feature inherent topolychromic solid films is also provided herein, making polychromicsolid films particularly attractive for use in connection withelectrochromic devices, such as mirrors, windows, sun roofs, shadebands, eye glass and the like.

Polychromic solid films embody a novel and useful technology within theelectrochromic art, whose utility will become more readily apparent andmore greatly appreciated by those of skill in the art through a study ofthe detailed description taken in conjunction with the figures whichfollow hereinafter.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a sectional view of an electrochromic device employing anelectrochromic polymeric solid film according to the present invention.

FIG. 2 depicts a perspective view of an electrochromic glazing assemblyaccording to the present invention.

The depictions in these figures are for illustrative purposes and thusare not drawn to scale.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the teaching of the present invention, polychromicsolid films may be prepared by exposing an electrochromic monomercomposition to electromagnetic radiation for a time sufficient totransform the electrochromic monomer composition into a polychromicsolid film. This in situ curing process initiates polymerization of, andtypically completely polymerizes, an electrochromic monomer composition,normally in a liquid state, by exposure to electromagnetic radiation toform a polychromic solid film, whose surface and cross-sections aresubstantially tack-free.

The electrochromic monomer compositions are comprised of anodicelectrochromic compounds, cathodic electrochromic compounds, each ofwhich are organic or organometallic compounds, a monomer component and aplasticizer. In addition, cross-linking agents, photoinitiators,photosensitizers, ultraviolet stabilizing agents, electrolyticmaterials, coloring agents, spacers, anti-oxidizing agents, flameretarding agents, heat stabilizing agents, compatibilizing agents,adhesion promoting agents, coupling agents, humectants and lubricatingagents and combinations thereof may also be added. In the preferredelectrochromic monomer compositions, the chosen monomer component may bea polyfunctional monomer, such as a difunctional monomer, trifunctionalmonomer, or a higher functional monomer, or a combination ofmonofunctional monomer and difunctional monomer or monofunctionalmonomer and cross-linking agent. Those of ordinary skill in the art maychoose a particular monomer component or combination of monomercomponents from those recited in view of the intended application so asto impart the desired beneficial properties and characteristics to thepolychromic solid film.

An anodic electrochromic compound suitable for use in the presentinvention may be selected from the class of chemical compoundsrepresented by the following formulae: ##STR1## wherein A is O, S orNRR₁ ;

wherein R and R₁ may be the same or different, and each may be selectedfrom the group consisting of H or any straight- or branched-chain alkylconstituent having from about one carbon atom to about eight carbonatoms, such as CH₃, CH₂ CH₃, CH₂ CH₂ CH₃, CH(CH₃)₂, C(CH₃)₃ and thelike; provided that when A is NRR₁, Q is H, OH or NRR₁ ; furtherprovided that when A is NRR₁, a salt may be associated therewith; stillfurther provided that when both A and Q are NRR₁, A and Q need not, butmay, be the same functional group;

D is O, S, NR₁ or Se;

E is R₁, COOH or CONH₂ ; or, E and T, when taken together, represent anaromatic ring structure having six ring carbon atoms when viewed inconjunction with the ring carbon atoms to which they are attached;

G is H;

J is H, any straight- or branched-chain alkyl constituent having fromabout one carbon atom to about eight carbon atoms, such as CH₃, CH₂ CH₃,CH₂ CH₂ CH₃, CH(CH₃)₂, C(CH₃)₃ and the like, NRR₁, ##STR2## OR₁, phenyl,2,4-dihydroxyphenyl or any halogen; or, G and J, when taken together,represent an aromatic ring structure having six ring carbon atoms whenviewed in conjunction with the ring carbon atoms to which they areattached;

L is H or OH;

M is H or any halogen;

T is R₁, phenyl or 2,4-dihydroxyphenyl; and

Q is H, OH or NRR₁ ;

provided that when L and/or Q are OH, L and/or Q may also be saltsthereof; further provided that in order to render it electrochemicallyactive in the present context, anodic electrochromic compound I has beenpreviously contacted with a redox agent; ##STR3## wherein X and Y may bethe same or different, and each may be selected from the groupconsisting of H, any halogen or NRR₁, wherein R and R₁ may be the sameor different, and are as defined supra; or, X and Y, when takentogether, represent an aromatic ring structure having six ring carbonatoms when viewed in conjunction with the ring carbon atoms to whichthey are attached; and

Z is OH or NRR₁, or salts thereof;

provided that in order to render it electrochemically active in thepresent context, anodic electrochromic compound II has been previouslycontacted with a redox agent; ##STR4## wherein R and R₁ may be the sameor different, and are defined supra; ##STR5## wherein R and R₁ may bethe same or different, and are defined supra; ##STR6## wherein R and R₁may be the same or different, and are defined supra; ##STR7## wherein Rand R₁ may be the same or different, and each may be selected from thegroup consisting of H or any straight- or branched-chain alkylconstituent having from about one carbon atom to about eight carbonatoms, such as CH₃, CH₂ CH₃, CH₂ CH₂ CH₃, CH(CH₃) ₂, C(CH₃)₃ and thelike; ##STR8## wherein R₂ may be H or CH₃ and n may be an integer in therange of 0 to 6; OH; COOH; and HO--(CH₂)_(n) --, wherein n may be aninteger in the range of 1 to 6;

M_(c) is Fe, Ni, Co, Ti, Cr, W, Mo and the like; ##STR9## andcombinations thereof.

To render anodic electrochromic compounds I and II electrochemicallyactive in the context of the present invention, a redox pre-contactingprocedure must be used. Such a redox pre-contacting procedure isdescribed in the context of preparing anodic compounds forelectrochemichromic solutions in Varaprasad IV and commonly assignedco-pending U.S. patent application Ser. No. 07/935,784 (filed Aug. 27,1992).

Preferably, anodic electrochromic compound I may be selected from thegroup consisting of the class of chemical compounds represented by thefollowing formulae: ##STR10## and combinations thereof.

Among the especially preferred anodic electrochromic compounds I areMVTB (XV), PT (XVI), MPT (XVII), and POZ (XIX), with MVTB and MPT beingmost preferred. Also preferred is the reduced form of MPT which resultsfrom the redox pre-contacting procedure referred to above, and has beenthereafter isolated. This reduced and isolated form of MPT--RMPT[XVII(a)]--is believed to be 2-methyl-3-hydroxyphenathiazine, which isrepresented by the following chemical formula ##STR11## and saltsthereof.

In addition, a preferred anodic electrochromic compound II is ##STR12##and salts thereof.

Likewise, preferred among anodic electrochromic compound III are5,10-dihydro-5,10-dimethylphenazine ("DMPA") and5,10-dihydro-5,10-diethylphenazine ("DEPA"), with DMPA beingparticularly preferred.

As a preferred anodic electrochromic compound VI, metallocenes, such asferrocene, wherein M_(c) is iron and R and R₁ are each hydrogen, andalkyl derivatives thereof, may also be used advantageously in thecontext of the present invention.

The salts referred to in connection with the anodic electrochromiccompounds include, but are not limited to, alkali metal salts, such aslithium, sodium, potassium and the like. In addition, when A is NRR₁,tetrafluoroborate ("BF₄ ⁻ "), perchlorate ("ClO₄ ⁻ "), trifluoromethanesulfonate ("CF₃ SO₃ ⁻ "), hexafluorophosphate ("PF₆ ⁻ "), acetate ("Ac⁻") and any halogen may be associated therewith. Moreover, the ringnitrogen atom in anodic electrochromic compound I may also appear as anN-oxide.

Any one or more of anodic electrochromic compounds I, II, III, IV, V, VIor VII may also be advantageously combined, in any proportion, within anelectrochromic monomer composition and thereafter transformed into apolychromic solid film to achieve the results so stated herein. Ofcourse, as regards anodic electrochromic compounds I and II, it isnecessary to contact those compounds with a redox agent prior to use soas to render them electrochemically active in the present invention.Upon the application of a potential thereto, such combinations of anodicelectrochromic compounds within a polychromic solid film may oftengenerate color distinct from the color observed from polychromic solidfilms containing individual anodic electrochromic compounds. A preferredcombination of anodic electrochromic compounds in this invention is thecombination of anodic electrochromic compounds III and VI. Nonetheless,those of ordinary skill in the art may make appropriate choices amongindividual anodic electrochromic compounds and combinations thereof, toprepare a polychromic solid film capable of generating a color suitablefor a particular application.

A choice of a cathodic electrochromic compound for use herein shouldalso be made. The cathodic electrochromic compound may be selected fromthe class of chemical compounds represented by the following formulae:##STR13## wherein R₃ and R₄ may be the same or different, and each maybe selected from the group consisting of H, any straight- orbranched-chain alkyl constituent having from about one carbon atom toabout eight carbon atoms, or any straight- or branched-chain alkyl oralkoxy-phenyl, wherein the alkyl or alkoxy constituent contains fromabout one carbon atom to about eight carbon atoms; ##STR14## wherein n'may be an integer in the range of 1 to 6; ##STR15## wherein R₅ may be Hor CH₃, and n' may be an integer in the range of 2 to 6; HO--(CH₂)_(n')--, wherein n' may be an integer in the range of 1 to 6; andHOOC--(CH₂)_(n') --, wherein n' may be an integer in the range of 1 to6; and

X is selected from the group consisting of BF₄ ⁻, ClO₄ ⁻, CF₃ SO₃ ⁻,styrylsulfonate ("SS⁻ "), 2-acrylamido-2-methylpropane-sulfonate,acrylate, methacrylate, 3-sulfopropylacrylate,3-sulfopropylmethacrylate, PF₆ ⁻, Ac⁻ and any halide; and ##STR16## andcombinations thereof.

Specific cathodic electrochromic compounds useful in the context of thepresent invention include: ##STR17##

Preferably, R₃ and R₄ are each ethyl or n-heptyl. Thus, when X is ClO₄ ⁻or BF₄ ⁶³¹ , preferred cathodic electrochromic compounds areethylviologen perchlorate ("EVClO₄ ") and heptylviologentetrafluoroborate ("HVBF₄ "), respectively.

The above anodic electrochromic compounds and cathodic electrochromiccompounds may be chosen so as to achieve a desired color when thepolychromic solid film in which they are present (and the device inwhich the polychromic solid film is contained) is colored to a dimmedstate. For example, electrochromic automotive mirrors manufactured withpolychromic solid films should preferably bear a blue or substantiallyneutral color when colored to a dimmed state. And, electrochromicoptically attenuating contrast filters, such as contrast enhancementfilters, manufactured with polychromic solid films should preferablybear a substantially neutral color when colored to a dimmed state.

The plasticizer chosen for use in the present invention should maintainthe homogeneity of the electrochromic monomer compositions while beingprepared, used and stored, and prior to, during and after exposure toelectromagnetic radiation. As a result of its combination within theelectrochromic monomer composition or its exposure to electromagneticradiation, the plasticizer of choice should not form by-products thatare capable of hindering, or interfering with, the homogeneity and theelectrochemical efficacy of the resulting polychromic solid film. Theoccurrence of any of these undesirable events during the in situ curingprocess, whether at the pre-cure, cure or post-cure phase of the processfor preparing polychromic solid films, may interfere with the processitself, and may affect the appearance and effectiveness of the resultingpolychromic solid films, and the electrochromic devices manufacturedwith the same. The plasticizer also may play a role in defining thephysical properties and characteristics of the polychromic solid filmsof the present invention, such as toughness, flex modulus, coefficientof thermal expansion, elasticity, elongation and the like.

Suitable plasticizers for use in the present invention include, but arenot limited to, acetonitrile, benzylacetone, 3-hydroxypropionitrile,methoxypropionitrile, 3-ethoxypropionitrile, propylene carbonate,ethylene carbonate, glycerine carbonate, 2-acetylbutyrolactone,cyanoethyl sucrose, γ-butyrolactone, 2-methylglutaronitrile,N,N'-dimethylformamide, 3-methylsulfolane, methylethyl ketone,cyclopentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone,acetophenone, glutaronitrile, 3,3,-oxydipropionitrile, 2-methoxyethylether, triethylene glycol dimethyl ether and combinations thereof.Particularly preferred plasticizers among that group are benzylacetone,3-hydroxypropionitrile, propylene carbonate, ethylene carbonate,2-acetylbutyrolactone, cyanoethyl sucrose, triethylene glycol dimethylether, 3-methylsulfolane and combinations thereof.

To prepare a polychromic solid film, a monomer should be chosen as amonomer component that is capable of in situ curing through exposure toelectromagnetic radiation, and that is compatible with the othercomponents of the electrochromic monomer composition at the variousstages of the in situ curing process. The combination of a plasticizerwith a monomer component (with or without the addition of a difunctionalmonomer or a cross-linking agent) should preferably be in an equivalentratio of between about 75:25 to about 10:90 to prepare polychromic solidfilms with superior properties and characteristics. Of course, theart-skilled should bear in mind that the intended application of apolychromic solid film will often dictate its particular properties andcharacteristics, and that the choice and equivalent ratio of thecomponents within the electrochromic monomer composition may need to bevaried to attain a polychromic solid film with the desired propertiesand characteristics.

Among the monomer components that may be advantageously employed in thepresent invention are monomers having at least one reactivefunctionality rendering the compound capable of polymerization orfurther polymerization by an addition mechanism, such as vinylpolymerization, or ring opening polymerization. Included among suchmonomers are oligomers and polymers that are capable of furtherpolymerization. For monomers suitable for use herein, see generallythose commercially available from Monomer-Polymer Labs., Inc.,Philadelphia, Pa.; Sartomer Co., Exton, Pa.; and Polysciences, Inc.,Warrington, Pa.

Monomers capable of vinyl polymerization, suitable for use herein, haveas a commonality the ethylene functionality, as represented below:##STR18## wherein R₆, R₇ and R₈ may be the same or different, and areeach selected from a member of the group consisting of hydrogen;halogen; alkyl, cycloalkyl, poly-cycloalkyl, heterocycloalkyl and alkyland alkenyl derivatives thereof; alkenyl, cycloalkenyl, cycloalkadienyl,poly-cycloalkadienyl and alkyl and alkenyl derivatives thereof;hydroxyalkyl; hydroxyalkenyl; alkoxyalkyl; alkoxyalkenyl; cyano; amido;phenyl; benzyl and carboxylate, and derivatives thereof.

Preferred among these vinyl monomers are the ethylene carboxylatederivatives known as acrylates--i.e., wherein at least one of R₆, R₇ andR₈ are carboxylate groups or derivatives thereof. Suitable carboxylatederivatives include, but are not limited to alkyl, cycloalkyl,poly-cycloalkyl, heterocycloalkyl and alkyl and alkenyl derivativesthereof; alkenyl, cycloalkenyl, poly-cycloalkenyl and alkyl and alkenylderivatives thereof; mono- and poly-hydroxyalkyl; mono- andpoly-hydroxyalkenyl; alkoxyalkyl; alkoxyalkenyl and cyano.

Among the acrylates that may be advantageously employed herein are mono-and poly-acrylates (bearing in mind that poly-acrylates function ascross-linking agents as well, see infra), such as 2-hydroxyethylacrylate, 2-hydroxyethyl methacrylate, methylene glycol monoacrylate,diethylene glycol monomethacrylate, 2-hydroxypropyl acrylate,2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropylmethacrylate, dipropylene glycol monomethacrylate, 2,3-dihydroxypropylmethacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate,i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, n-pentylacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylmethacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butylmethacrylate, s-butyl methacrylate, n-pentyl methacrylate, s-pentylmethacrylate, methoxyethyl acrylate, methoxyethyl methacrylate,triethylene glycol monoacrylate, glycerol monoacrylate, glycerolmonomethacrylate, allyl methacrylate, benzyl acrylate, caprolactoneacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethoxyethylacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethylacrylate,glycidyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, isobornylacrylate, isobornyl methacrylate, i-decyl acrylate, i-decylmethacrylate, i-octyl acrylate, lauryl acrylate, lauryl methacrylate,2-methoxyethyl acrylate, n-octyl acrylate, 2-phenoxyethyl acrylate,2-phenoxyethyl methacrylate, stearyl acrylate, stearyl methacrylate,tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tridecylmethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate,1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate,diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethyleneglycol diacrylate, ethoxylated bisphenol A dimethacrylate, ethyleneglycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, polyethylene glycol diacrylate, polyethylene glycoldimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, triethylene glycol diacrylate, triethylene glycoldimethacrylate, tripropylene glycol diacrylate, dipentaerythritolpentaacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritoltetraacrylate, pentaerythritol triacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate,tris(2-hydroxyethyl)-isocyanurate triacrylate,tris(2-hydroxyethyl)-isocyanurate trimethacrylate, polyethylene glycolmonoacrylate, polyethylene glycol monomethacrylate, polypropylene glycolmonoacrylate, polypropylene glycol monomethacrylate, hydroxyethylcellulose acrylate, hydroxyethyl cellulose methacrylate, methoxypoly(ethyleneoxy) ethylacrylate, methoxy poly(ethyleneoxy)ethylmethacrylate and combinations thereof. For a further recitation ofsuitable acrylates for use herein, see those acrylates availablecommercially from Monomer-Polymer Labs, Inc.; Polysciences, Inc. andSartomer Co. Also, those of ordinary skill in the art will appreciatethat derivatized acrylates in general should provide beneficialproperties and characteristics to the resulting polychromic solid film.

Other monomers suitable for use herein include styrenes, unsaturatedpolyesters, vinyl ethers, acrylamides, methyl acrylamides and the like.

Monomers capable of ring opening polymerization suitable for use hereininclude epoxides, lactones, lactams, dioxepanes, spiro orthocarbonates,unsaturated spiro orthoesters and the like.

Preferred among these ring opening polymerizable monomers are epoxidesand lactones. Of the epoxides suitable for use herein, preferred arecyclohexene oxide, cyclopentene oxide, glycidyl i-propyl ether, glycidylacrylate, furfuryl glycidyl ether, styrene oxide, ethyl-3-phenylglycidate, 1,4-butanediol glycidyl ether,2,3-epoxypropyl-4-(2,3-epoxypropoxy) benzoate,4,4'-bis-(2,3-epoxypropoxy)biphenyl and the like.

Also, particularly preferred are the cycloalkyl epoxides sold under the"CYRACURE" tradename by Union Carbide Chemicals and Plastics Co., Inc.,Danbury, Conn., such as the "CYRACURE" resins UVR-6100 (mixed cycloalkylepoxides), UVR-6105 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), UVR-6110 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate) and UVR-6128 [bis-(3,4-epoxycyclohexyl)adipate], and the"CYRACURE" diluents UVR-6200 (mixed cycloalkyl epoxides) and UVR-6216(1,2-epoxyhexadecane); those epoxides commercially available from DowChemical Co., Midland, Mich., such as D.E.R. 736 epoxy resin(epichlorohydrin-polyglycol reaction product), D.E.R. 755 epoxy resin(diglycidyl ether of bisphenol A-diglycidyl ether of polyglycol) andD.E.R. 732 epoxy resin (epichlorohydrin-polyglycol reaction product),and the NOVOLAC epoxy resins such as D.E.N. 431, D.E.N. 438 and D.E.N.439 (phenolic epoxides), and those epoxides commercially available fromShell Chemical Co., Oak Brook, Ill., like the "EPON" resins 825 and1001F (epichlorohydrin-bisphenol A type epoxy resins).

Other commercially available epoxide monomers that are particularlywell-suited for use herein include those commercially available underthe "ENVIBAR" tradename from Union Carbide Chemicals and Plastics Co.,Inc., Danbury, Conn., such as "ENVIBAR" UV 1244 (cycloalkyl epoxides).

In addition, derivatized urethanes, such as acrylated (e.g., mono- orpoly-acrylated) urethanes; derivatized heterocycles, such as acrylated(e.g., mono- or poly-acrylated) heterocycles, such as acrylatedepoxides, acrylated lactones, acrylated lactams; and combinationsthereof, capable of undergoing addition polymerizations, such as vinylpolymerizations and ring opening polymerizations, are also well-suitedfor use herein.

Many commercially available ultraviolet curable formulations arewell-suited for use herein as a monomer component in the electrochromicmonomer composition. Among those commercially available ultravioletcurable formulations are acrylated urethanes, such as the acrylatedalkyl urethane formulations commercially available from Sartomer Co.,including Low Viscosity Urethane Acrylate (Flexible) (CN 965), LowViscosity Urethane Acrylate (Resilient) (CN 964), Urethane Acrylate (CN980), Urethane Acrylate/TPGDA (CN 966 A80), Urethane Acrylate/IBOA (CN966 J75), Urethane Acrylate/EOEOEA (CN 966 H90), Urethane Acrylate/TPGDA(CN 965 A80), Urethane Acrylate/EOTMPTA (CN 964 E75), UrethaneAcrylate/EOEOEA (CN 966 H90), Urethane Acrylate/TPGDA (CN 963 A80),Urethane Acrylate/EOTMPTA (CN 963 E75), Urethane Acrylate (Flexible) (CN962), Urethane Acrylate/EOTMPTA (CN 961 E75), Urethane Acrylate/EOEOEA(CN 961 H90), Urethane Acrylate (Hard) (CN 955), Urethane Acrylate(Hard) (CN 960) and Urethane Acrylate (Soft) (CN 953), and acrylatedaromatic urethane formulations, such as those sold by Sartomer Co., mayalso be used herein, including Hydrophobic Urethane Methacrylate (CN974), Urethane Acrylate/TPGDA (CN 973 A80), Urethane Acrylate/IBOA (CN973 J75), Urethane Acrylate/EOEOEA (CN 973 H90), Urethane Acrylate(Flexible) (CN 972), Urethrane Acrylate (Resilient) (CN 971), UrethaneAcrylate/TPGDA (CN 971 A80), Urethane Acrylate/TPGDA (CN 970 A60),Urethane Acrylate/EOTMPTA (CN 970 E60) and Urethane Acrylate/EOEOEA (CN974 H75). Other acrylated urethane formulations suitable for use hereinmay be obtained commercially from Monomer-Polymer Labs, Inc. andPolysciences, Inc.

Other ultraviolet curable formulations that may be used herein are theultraviolet curable acrylated epoxide formulations commerciallyavailable from Sartomer Co., such as Epoxidized Soy Bean Oil Acrylate(CN 111), Epoxy Acrylate (CN 120), Epoxy Acrylate/TPGDA (CN 120 A75),Epoxy Acrylate/HDDA (CN 120 B80), Epoxy Acrylate/TMPTA (CN 120 C80),Epoxy Acrylate/GPTA (CN 120 D80), Epoxy Acrylate/Styrene (CN 120 S85),Epoxy Acrylate (CN 104), Epoxy Acrylate/GPTA (CN 104 D80), EpoxyAcrylate/HDDA (CN 104 B80), Epoxy Acrylate/TPGDA (CN 104 A80), EpoxyAcrylate/TMPTA (CN 104 C75), Epoxy Novolac Acrylate/TMPTA (CN 112 C60),Low Viscosity Epoxy Acrylate (CN 114), Low Viscosity EpoxyAcrylate/EOTMPTA (CN 114 E80), Low Viscosity Epoxy Acrylate/GPTA (CN 114D75) and Low Viscosity Epoxy Acrylate/TPGDA (CN 114 A80).

In addition, "SARBOX" acrylate resins, commercially available fromSartomer Co., like Carboxylated Acid Terminated (SB 400), CarboxylatedAcid Terminated (SB 401), Carboxylated Acid Terminated (SB 500),Carboxylated Acid Terminated (SB 5OE50), Carboxylated Acid Terminated(SB 500K60), Carboxylated Acid Terminated (SB 501), Carboxylated AcidTerminated (SB 510E35), Carboxylated Acid Terminated (SB 520E35) andCarboxylated Acid Terminated (SB 600) may also be advantageouslyemployed herein.

Also well-suited for use herein are ultraviolet curable formulationslike the ultraviolet curable acrylated epoxy urethane conformationalcoating formulations commercially available under the "QUICK CURE"trademark from the Specialty Coating Systems subsidiary of Union CarbideChemicals & Plastics Technology Corp., Indianapolis, Ind., and soldunder the product designations B-565, B-566, B-576 and BT-5376;ultraviolet curing acrylate adhesive formulations commercially availablefrom Loctite Corp., Newington, Conn. under the product names UVOPTICALLY CLEAR ADH, MULTI PURPOSE UV ADHESIVE, "IMPRUV" LV POTTINGCOMPOUND and "LOCQUIC" ACTIVATOR 707; ultraviolet curable urethaneformulations commercially available from Norland Products, Inc., NewBrunswick, N.J., and sold under the product designations "NORLAND NOA61", "NORLAND NOA 65" and "NORLAND NOA 68"; and ultraviolet curableacrylic formulations commercially available from Dymax Corp.,Torrington, Conn., including "DYMAX LIGHT-WELD 478".

By employing polyfunctional monomers, like difunctional monomers, orcross-linking agents, cross-linked polychromic solid films may beadvantageously prepared. Such cross-linking tends to improve thephysical properties and characteristics (e.g., mechanical strength) ofthe resulting polychromic solid films. Cross-linking during cure totransform the electrochromic monomer composition into a polychromicsolid film may be achieved by means of free radical ionic initiation bythe exposure to electromagnetic radiation. This may be accomplished bycombining together all the components of the particular electrochromicmonomer composition and thereafter effecting cure. Alternatively,cross-links may be achieved by exposing to electromagnetic radiation theelectrochromic monomer composition for a time sufficient to effect apartial cure, whereupon further electromagnetic radiation and/or athermal influence may be employed to effect a more complete in situ cureand transformation into the polychromic solid film.

Suitable polyfunctional monomers for use in preparing polychromic filmsshould have at least two reactive functionalities, and may be selectedfrom, among others, ethylene glycol diacrylate, ethylene glycoldimethacrylate, 1,2-butylene dimethacrylate, 1,3-butylenedimethacrylate, 1,4-butylene dimethacrylate, propylene glycoldiacrylate, propylene glycol dimethacrylate, diethylene glycoldiacrylate, dipropylene glycol diacrylate, divinyl benzene, divinyltoluene, diallyl tartrate, allyl maleate, divinyl tartrate, triallylmelamine, glycerine trimethacrylate, diallyl maleate, divinyl ether,diallyl monomethylene glycol citrate, ethylene glycol vinyl allylcitrate, allyl vinyl maleate, diallyl itaconate, ethylene glycol diesterof itaconic acid, polyester of maleic anhydride with triethylene glycol,polyallyl glucoses (e.g., triallyl glucose), polyallyl sucroses (e.g.,pentaallyl sucrose diacrylate), glucose dimethacrylate, pentaerythritoltetraacrylate, sorbitol dimethacrylate, diallyl aconitate, divinylcitrasonate, diallyl fumarate, allyl methacrylate and polyethyleneglycol diacrylate.

Ultraviolet radiation absorbing monomers may also be advantageouslyemployed herein. Preferred among such monomers are1,3-bis-(4-benzoyl-3-hydroxyphenoxy)-2-propylacrylate,2-hydroxy-4-acryloxyethoxybenzophenone, 2-hydroxy-4-octoxybenzophenoneand 4-methacryloxy-2-hydroxybenzophenone, as they perform the dualfunction of acting as a monomer component, or a portion thereof, and asan ultraviolet stabilizing agent.

The density of the cross-link within the resulting polychromic solidfilm tends to increase with the amount and/or the degree offunctionality of polyfunctional monomer present in the electrochromicmonomer composition. Cross-linking density within a polychromic solidfilm may be achieved or further increased by adding to theelectrochromic monomer composition cross-linking agents, whichthemselves are incapable of undergoing further polymerization. Inaddition to increasing the degree of cross-linking within the resultingpolychromic solid film, the use of such cross-linking agents in theelectrochromic monomer composition may enhance the prolonged colorationperformance of the resulting polychromic solid film. Included among suchcross-linking agents are polyfunctional hydroxy compounds, such asglycols and glycerol, polyfunctional primary or secondary aminocompounds and polyfunctional mercapto compounds. Among the preferredcross-linking agents are pentaerythritol,2-ethyl-2-(hydroxymethyl)-1,3-propanediol, the poly (caprolactone) diolshaving molecular weights of 1,250, 2,000 and 3,000, and polycarbonatediol available from Polysciences, Inc. and the polyfunctional hydroxycompounds commercially available under the "TONE" tradename from UnionCarbide Chemicals and Plastics Co. Inc., Danbury, Conn., such asE-caprolactone triols (known as "TONE" 0301, "TONE" 0305 and "TONE"0310). Among the preferred glycols are the poly(ethylene glycols), likethose sold under the "CARBOWAX" tradename by the Industrial Chemicaldivision of Union Carbide Corp., Danbury, Conn. such as "CARBOWAX" PEG200, PEG 300, PEG 400, PEG 540 Blend, PEG 600, PEG 900, PEG 1000, PEG1450, PEG 3350, PEG 4600, and PEG 8000, with "CARBOWAX" PEG 1450 beingthe most preferred among this group, and those available fromPolysciences, Inc.

Polychromic solid films that perform well under prolonged coloration maybe prepared from electrochromic monomer compositions that contain as amonomer component at least some portion of a polyfunctionalmonomer--e.g., a difunctional monomer. By preferably usingpolyfunctional monomers having their functional groups spaced apart tosuch an extent so as to enhance the flexibility of the resultingpolychromic solid film, polychromic solid films may be prepared with aminimum of shrinkage during the transformation process and that alsoperform well under prolonged coloration.

While it is preferable to have electrochromic monomer compositions whichcontain a monomer component having polyfunctionality in preparingpolychromic solid films that perform well under prolonged coloration,electrochromic monomer compositions that exhibit enhanced resistance toshrinkage when transformed into polychromic solid films preferablycontain certain monofunctional monomers. In this regard, depending onthe specific application, some physical properties and characteristicsof polychromic solid films may be deemed of greater import than others.Thus, superior performance in terms of resistance to shrinkage during insitu curing of the electrochromic monomer composition to the polychromicsolid film may be balanced with the prolonged coloration performance ofthe resulting polychromic solid film to achieve the properties andcharacteristics desirable of that polychromic solid film.

Those of ordinary skill in the art may make appropriate choices amongthe herein described monomers--monofunctional and polyfunctional, suchas difunctional--and cross-linking agents to prepare a polychromic solidfilm having beneficial properties and characteristics for the specificapplication by choosing such combinations of a monofunctional monomer toa polyfunctional monomer or a monofunctional monomer to a cross-linkingagent in an equivalent ratio of about 1:1 or greater.

In the preferred electrochromic monomer compositions, photoinitiators orphotosensitizers may also be added to assist the initiation of the insitu curing process. Such photoinitiators or photosensitizers enhancethe rapidity of the curing process when the electrochromic monomercompositions are exposed to electromagnetic radiation. These materialsinclude, but are not limited to, radical initiation type and cationicinitiation type polymerization initiators such as benzoin derivatives,like the n-butyl, i-butyl and ethyl benzoin alkyl ethers, and thosecommercially available products sold under the "ESACURE" tradename bySartomer Co., such as "ESACURE" TZT (trimethyl benzophenone blend), KB1(benzildimethyl ketal), KB60 (60% solution of benzildimethyl ketal), EB3(mixture of benzoin n-butyl ethers), KIP 100F (α-hydroxy ketone), KT37(TZT and α-hydroxy ketone blend), ITX (i-propylthioxanthone), X15 (ITXand TZT blend), and EDB [ethyl-4-(dimethylamino)-benzoate]; thosecommercially available products sold under the "RGACURE" and "DAROCURE"tradenames by Ciba Geigy Corp., Hawthorne, N.Y., specifically "IRGACURE"184, 907, 369, 500, 651, 261, 784 and "DAROCURE" 1173 and 4265,respectively; the photoinitiators commercially available from UnionCarbide Chemicals and Plastics Co. Inc., Danbury, Conn., under the"CYRACURE" tradename, such as "CYRACURE" UVI-6974 (mixed triarylsulfonium hexafluoroantimonate salts) and UVI-6990 (mixed triarylsulfonium hexafluorophosphate salts); and the visible light [blue]photoinitiator, dl-camphorquinone.

Of course, when those of ordinary skill in the art choose a commerciallyavailable ultraviolet curable formulation, it may no longer be desirableto include as a component within the electrochromic monomer compositionan additional monomer to that monomer component already present in thecommercial formulation. And, as many of such commercially availableultraviolet curable formulations contain a photoinitiator orphotosensitizer, it may no longer be desirable to include this optionalcomponent in the electrochromic monomer composition. Nevertheless, amonomer, or a photoinitiator or a photosensitizer, may still be added tothe electrochromic monomer composition to achieve beneficial results,and particularly when specific properties and characteristics aredesired of the resulting polychromic solid film.

With an eye toward maintaining the homogeneity of the electrochromicmonomer composition and the polychromic solid film which results afterin situ cure, those of ordinary skill in the art should choose theparticular components dispersed throughout, and their relativequantities, appropriately. One or more compatibilizing agents may beoptionally added to the electrochromic monomer composition so as toaccomplish this goal. Such compatibilizing agents include, among others,combinations of plasticizers recited herein, a monomer component havingpolyfunctionality and cross-linking agents that provide flexiblecross-links. See supra.

Many electrochromic compounds absorb electromagnetic radiation in theabout 290 nm to about 400 nm ultraviolet region. Because solar radiationincludes an ultraviolet region between about 290 nm to about 400 nm, itis often desirable to shield such electrochromic compounds fromultraviolet radiation in that region. By so doing, the longevity andstability of the electrochromic compounds may be improved. Also, it isdesirable that the polychromic solid film itself be stable toelectromagnetic radiation, particularly in that region. This may beaccomplished by adding to the electrochromic monomer composition anultraviolet stabilizing agent (and/or a self-screening plasticizer whichmay act to block or screen such ultraviolet radiation) so as to extendthe functional lifetime of the resulting polychromic solid film. Suchultraviolet stabilizing agents (and/or self-screening plasticizers)should be substantially transparent in the visible region and functionto absorb ultraviolet radiation, quench degradative free radicalreaction formation and prevent degradative oxidative reactions.

As those of ordinary skill in the art will readily appreciate, thepreferred ultraviolet stabilizing agents, which are usually employed ona by-weight basis, should be selected so as to be compatible with theother components of the electrochromic monomer composition, and so thatthe physical, chemical or electrochemical performance of, as well as thetransformation into, the resulting polychromic solid film is notadversely affected.

Although many materials known to absorb ultraviolet radiation may beemployed herein, preferred ultraviolet stabilizing agents include"UVINUL" 400 [2,4-dihydroxy-benzophenone (manufactured by BASF Corp.,Wyandotte, Mich.)], "UVINUL" D 49[2,2'-dihydroxy-4,4'-dimethoxybenzophenone (BASF Corp.)], "UVINUL" N 35[ethyl-2-cyano-3,3-diphenylacrylate (BASF Corp.)], "UVINUL" N 539[2-ethylhexyl-2-cyano-3,3'-diphenylacrylate (BASF Corp.)], "UVINUL" M 40[2-hydroxy-4-methoxybenzophenone (BASF Corp.)], "UVINUL" M 408[2-hydroxy-4-octoxybenzophenone (BASF Corp.)], "TINUVIN" P[2-(2'-hydroxy-5'-methylphenyl)-triazole] (Ciba Geigy Corp.)], "TINTVIN"327 [2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole (CibaGeigy Corp.)], "TINUVIN" 328[2-(3',5'-di-n-pentyl-2'-hydroxyphenyl)-benzotriazole (Ciba GeigyCorp.)] and "CYASORB UV" 24 [2,2-dihydroxy-4-methoxy-benzophenone(manufactured by American Cyanamid Co., Wayne, N.J.)], with "UVINUL" M40, "UVINUL M" 408, "UVINUL" N 35 and "UVINUL" N 539 being the mostpreferred ultraviolet stabilizing agents when used in a by-weight rangeof about 0.1% to about 15%, with about 4% to about 10% being preferred.

Since solar radiation includes an ultraviolet region only between about290 nm and 400 nm, the cure wave length of the electrochromic monomercomposition, the peak intensity of the source of electromagneticradiation, and the principle absorbance maxima of the ultravioletstabilizing agents should be selected to provide a rapid and efficienttransformation of the electrochromic monomer compositions into thepolychromic solid films, while optimizing the continued long-termpost-cure stability to outdoor weathering and all-climate exposure ofpolychromic solid films.

An electrolytic material may also be employed in the electrochromicmonomer composition to assist or enhance the conductivity of theelectrical current passing through the resulting polychromic solid film.The electrolytic material may be selected from a host of knownmaterials, preferred of which are tetraethylammonium perchlorate,tetrabutylammonium tetrafluoroborate, tetrabutylammoniumhexafluorophosphate, tetrabutylammonium trifluoromethane sulfonate,lithium salts and combinations thereof, with tetrabutylammoniumhexafluorophosphate and tetraethylammonium perchlorate being the mostpreferred.

In addition, adhesion promoting agents or coupling agents may be used inthe preferred electrochromic monomer compositions to further enhance thedegree to which the resulting polychromic solid films adhere to thecontacting surfaces. Adhesion promoting or coupling agents, whichpromote such enhanced adhesion, include silane coupling agents, andcommercially available adhesion promoting agents like those sold bySartomer Co., such as Alkoxylated Trifunctional Acrylate (9008),Trifunctional Methacrylate Ester (9010 and 9011), Trifunctional AcrylateEster (9012), Aliphatic Monofunctional Ester (9013 and 9015) andAliphatic Difunctional Ester (9014). Moreover, carboxylated vinylmonomers, such as methacrylic acid, vinyl carboxylic acid and the likemay be used to further assist the development of good adhesion to thecontacting surfaces.

And, coloring agents, spacers, anti-oxidizing agents, flame retardingagents, heat stabilizing agents and combinations thereof may be added tothe electrochromic monomer compositions, choosing of course thosematerials in appropriate quantities depending upon the specificapplication of the resulting polychromic solid film. For instance, ablue-tinted electrochromic automotive mirror, such as described herein,may be prepared by dispersing within the electrochromic monomercomposition a suitable ultraviolet stable coloring agent, such as"NEOZAPON" BLUE TM 807 (a phthalocyanine blue dye, availablecommercially from BASF Corp., Parsippany, N.J.) and "NEOPEN" 808 (aphthalocyanine blue dye, available commercially from BASF Corp.).

Polychromic solid films may be prepared within an electrochromic deviceby introducing an electrochromic monomer composition to a film formingmeans, such as the vacuum backfilling technique, which fills a cavity ofan assembly by withdrawing into the cavity the electrochromic monomercomposition while the assembly is in an environment of reducedatmospheric pressure [see e.g., Varaprasad II], the two hole fillingtechnique, where the electrochromic monomer composition is dispensedunder pressure into the assembly through one hole while a gentle vacuumis applied at the other hole [see e.g., Varaprasad III], or with thesandwich lamination technique, which contemporaneously creates and fillsa cavity of an assembly by placing on one or both substrates either athermoplastic sealing means to act as a spacing means [see commonlyassigned U.S. Pat. No. 5,233,461 (Dornan)] or glass beads of nominaldiameter, and then exposing to electromagnetic radiation at least oneclear substrate of the assembly constructed by any of the abovemanufacturing techniques (containing the low viscosity electrochromicmonomer composition) for a time sufficient to transform theelectrochromic monomer composition into a polychromic solid film.

In connection with such film forming means, spacers, such as glassbeads, may be dispensed across the conductive surface of one or bothsubstrates, or dispersed throughout the electrochromic monomercomposition which may then be dispensed onto the conductive surface ofone or both substrates, to assist in preparing a polychromic solid filmwhich contacts, in abutting relationship, the conductive surface of thetwo substrates. Similarly, a pre-established spacing means of solidmaterial, such as tape, pillars, walls, ridges and the like, may also beemployed to assist in determining the interpane distance between thesubstrates in which a polychromic solid film may be prepared to contact,in abutting relationship with, the conductive surface of the twosubstrates.

Polychromic solid films may also be prepared separately from theelectrochromic device, and thereafter placed between, and in abuttingrelationship with, the conductive surface of the two substrates used inconstructing the device. Many known film manufacturing processes may beemployed as a film forming means to manufacture polychromic solid films.Included among these processes are calendering, casting, rolling,dispensing, coating, extrusion and thermoforming. For a non-exhaustivedescription of such processes, see Modern Plastics Encyclopedia 1988,203-300, McGraw-Hill Inc., New York (1988). For instance, theelectrochromic monomer composition may be dispensed or coated onto theconductive surface of a substrate, using conventional techniques, suchas curtain coating, spray coating, dip coating, spin coating, rollercoating, brush coating or transfer coating.

As described above, polychromic solid films may be prepared as aself-supporting solid film which may thereafter be contacted withconductive substrates.

For instance, an electrochromic monomer composition may be continuouslycast or dispensed onto a surface, such as a fluorocarbon surface and thelike, to which the polychromic solid film, transformed therefrom byexposure to electromagnetic radiation, does not adhere In this way,polychromic solid films may be continously prepared, and, for example,reeled onto a take-up roller and stored for future use. Thus, when aparticular electrochromic device is desired, an appropriately shapedportion of the stored polychromic solid film may be cut from the rollusing a die, laser, hot wire, blade or other cutting means. This nowcustom-cut portion of polychromic solid film may be contacted with theconductive substrates to form an electrochromic device.

For example, the custom-cut portion of the polychromic solid film may belaminated between the conductive surface of two transparent conductivecoated substrates, such as ITO or tin oxide coated glass substrates, twoITO or tin oxide coated "MYLAR" [polyethylene terephthalate film(commercially available from E. I. du Pont de Nemours and Co.,Wilmington, Del.)] substrates or one ITO or tin oxide coated glasssubstrate and one ITO or tin oxide coated "MYLAR" substrate. To thisend, it may be desirable to allow for residual cure in the storedpolychromic solid film so that adhesion to the conductive substrates inthe laminate to be formed is facilitated and optimized.

In this regard, a polychromic solid film may be prepared by the filmforming means of extrusion or calendaring wherein the electrochromicmonomer composition is transformed into the polychromic solid film byexposure to electromagnetic radiation prior to, contemporaneously with,or, if the electrochromic monomer composition is sufficiently viscous,after passing through the extruder or calendar. :hereafter, thepolychromic solid film may be placed between, and in abuttingrelationship with, the conductive surface of the substrates, and thenconstruction of the electrochromic device may be completed.

While preparing polychromic solid films, the viscosity of theelectrochromic monomer composition may be controlled to optimize itsdispensibility by adjusting the temperature of (1) the electrochromicmonomer composition itself, (2) the substrates on which theelectrochromic monomer composition may be placed to assemble theelectrochromic device or (3) the processing equipment used to preparepolychromic solid films (if the polychromic film is to be preparedindependently from the substrates of the electrochromic devices). Forexample, the temperature of the electrochromic monomer composition, thesubstrates or the equipment or combinations thereof may be elevated todecrease the viscosity of the electrochromic monomer composition.Similarly, the uniformity on the substrate of the dispensedelectrochromic monomer composition may be enhanced using laminationtechniques, centrifuge techniques, pressure applied from the atmosphere(such as with vacuum bagging), pressure applied from a weighted object,rollers and the like.

The substrates employed in the electrochromic devices of the presentinvention may be constructed from materials that are substantiallyinflexible as well as flexible depending on the application to whichthey are to be used. In this regard, the substrates may be constructedfrom substantially inflexible substrates, such as glass, laminatedglass, tempered glass, optical plastics, such as polycarbonate, acrylicand polystyrene, and flexible substrates, such as "MYLAR" film. Also,the glass substrates suitable for use herein may be tinted specializedglass which is known to significantly reduce ultraviolet radiationtransmission while maintaining high visible light transmission. Suchglass, often bearing a blue colored tint, provides a commerciallyacceptable silvery reflection to electrochromic automotive mirrors evenwhen the polychromic solid film is prepared containing an ultravioletstabilizing agent or other component which may have a tendency to imbuea yellowish appearance to the polychromic solid film. Preferably, bluetinted specialized glass may be obtained commercially from PittsburghPlate Glass Industries, Pittsburgh, Pa. as "SOLEXTRA" 7010; Ford GlassCo., Detroit, Mich. as "SUNGLAS" Blue; or Asahi Glass Co., Tokyo, Japanunder the "SUNBLUE" tradename.

Whether the chosen substrate is substantially inflexible or flexible, atransparent conductive coating, such as indium tin oxide ("ITO") ordoped-tin oxide, is coated on a surface of the substrate making thatsurface suitable for placement in abutting relationship with apolychromic solid film.

The choice of substrate may influence the choice of processingtechniques used to prepare the polychromic solid film or the type ofelectrochromic device assembled. For example, when assembling anelectrochromic device from flexible substrates, an electrochromicmonomer composition may be advantageously applied to such flexiblesubstrates using a roll-to-roll system where the flexible substrates arereleased from rolls (that are aligned and rotate in directions oppositeto one another), and brought toward one another in a spaced-apartrelationship. In this way, the electrochromic monomer composition may bedispensed or injected onto one of the flexible substrates at the pointwhere the two flexible substrates are released from their respectiverolls and brought toward one another, while being contemporaneouslyexposed to electromagnetic radiation for a time sufficient to transformthe electrochromic monomer composition into a polychromic solid film.

The dispensing of the electrochromic monomer composition may be effectedthrough a first injection nozzle positioned over one of the rolls offlexible substrate. A weathering barrier forming material, such as acuring epoxide like an ultraviolet curing epoxide, may be dispensed inan alternating and synchronized manner onto that flexible substratethrough a second injection nozzle positioned adjacent to the firstinjection nozzle. By passing in the path of these nozzles as acontinuously moving ribbon, a flexible substrate may be contacted withthe separate polymerizable compositions in appropriate amounts andpositions on the flexible substrate.

In manufacturing flexible electrochromic assemblies having a dimensionthe full width of the roll of flexible substrate, a weathering barrierforming material may be dispensed from the second injection nozzle whichmay be positioned inboard (typically about 2 mm to about 25 mm) from theleftmost edge of the roll of flexible substrate. The first injectionnozzle, positioned adjacent to the second injection nozzle, may dispensethe electrochromic monomer composition onto most of the full width ofthe roll of flexible substrate. A third injection nozzle, alsodispensing weathering barrier forming material, may be positionedadjacent to, but inboard from, the rightmost edge of that roll offlexible substrate (typically about 2 mm to about 25 mm). In thismanner, and as described above, a continuous ribbon of a flexibleelectrochromic assembly may be formed (upon exposure to electromagneticradiation) which, in turn, may be taken up onto a take-up roller. By sodoing, a flexible electrochromic assembly having the width of the rollof flexible substrate, but of a particular length, may be obtained byunrolling and cutting to length an electrochromic assembly of aparticular size.

Should it be desirable to have multiple flexible electrochromicassemblies positioned in the same taken-up roll, multiple nozzles may beplaced appropriately at positions throughout the width of one of therolls of flexible substrate, and the dispensing process carried outaccordingly.

In that regard, a small gap (e.g., about 5 mm to about 50 mm) should bemaintained where no dispensing occurs during the introduction of theelectrochromic monomer composition and the weathering barrier formingmaterial onto the substrate so that a dead zone is created where neitherthe electrochromic monomer composition nor the weathering barrierforming material is present. Once the weathering barrier and polychromicsolid film have formed (see infra), the electrochromic assembly may beisolated by cutting along the newly created dead zones of the flexibleassemblies. This zone serves conveniently as a cutting area to formelectrochromic assemblies of desired sizes.

And, the zones outboard of the respective weathering barriers serve asconvenient edges for attachment of a means for introducing an appliedpotential to the flexible electrochromic assemblies, such as bus bars.Similarly, the bisection of the dead zones establishes a convenientposition onto which the bus bars may be affixed.

While each of the weathering barrier forming material and theelectrochromic monomer composition may be transformed into a weatheringbarrier and a polychromic solid film, respectively, by exposure toelectromagnetic radiation, the required exposures to complete therespective transformations may be independent from one another. Theweathering barrier forming material may also be thermally cured to formthe weathering barrier.

The choice of a particular electromagnetic radiation region to effect insitu cure may depend on the particular electrochromic monomercomposition to be cured. In this regard, typical sources ofelectromagnetic radiation, such as ultraviolet radiation, include:mercury vapor lamps; xenon arc lamps; "H", "D", "X", "M", "IV" and "A"fusion lamps (such as those commercially available from Fusion UV CuringSystems, Buffalo Grove, Ill.); microwave generated ultravioletradiation; solar power and fluorescent light sources. Any of theseelectromagnetic radiation sources may use in conjunction therewithreflectors and filters, so as to focus the emitted radiation within aparticular electromagnetic region. Similarly, the electromagneticradiation may be generated directly in a steady fashion or in anintermittent fashion so as to minimize the degree of heat build-up.Although the region of electromagnetic radiation employed to in situcure the electrochromic monomer compositions into polychromic solidfilms is often referred to herein as being in the ultraviolet region,that is not to say that other regions of radiation within theelectromagnetic spectrum may not also be suitable. For instance, incertain situations, visible radiation may also be advantageouslyemployed.

Bearing in mind that some or all of the components of the electrochromicmonomer composition may inhibit, retard or suppress the in situ curingprocess, a given source of electromagnetic radiation should have asufficient intensity to overcome the inhibitive effects of thosecomponents so as to enable to proceed successfully the transformation ofthe electrochromic monomer composition into the polychromic solid film.By choosing a lamp with a reflector and, optionally, a filter, a sourcewhich itself produces a less advantageous intensity of electromagneticradiation may suffice. In any event, the chosen lamp preferably has apower rating of at least about 100 watts per inch (about 40 watts percm), with a power rating of at least about 300 watts per inch (about 120watts per cm) being particularly preferred. Most preferably, thewavelength of the lamp and its output intensity should be chosen toaccommodate the presence of ultraviolet stabilizing agents incorporatedinto electrochromic monomer compositions. Also, a photoinitiator orphotosensitizer, if used, may increase the rate of in situ curing orshift the wavelength within the electromagnetic radiation spectrum atwhich in situ curing will occur in the transformation process.

During the in situ curing process, the electrochromic monomercomposition will be exposed to a source of electromagnetic radiationthat emits an amount of energy, measured in KJ/m², determined byparameters including: the size, type and geometry of the source; theduration of the exposure to electromagnetic radiation; the intensity ofthe radiation (and that portion of radiation emitted within the regionappropriate to effect curing); the absorbance of electromagneticradiation by any intervening materials, such as substrates, conductivecoatings and the like; and the distance the electrochromic monomercomposition lies from the source of radiation. Those of ordinary skillin the art will readily appreciate that the polychromic solid filmtransformation may be optimized by choosing appropriate values for theseparameters in view of the particular electrochromic monomer composition.

The source of electromagnetic radiation may remain stationary while theelectrochromic monomer composition passes through its path.Alternatively, the electrochromic monomer composition may remainstationary while the source of electromagnetic radiation passesthereover or therearound to complete the transformation into apolychromic solid film. Still alternatively, both may traverse oneanother, or for that matter remain stationary, provided that theelectrochromic monomer composition is exposed to the electrochromicradiation for a time sufficient to effect such in situ curing.

Commercially available curing systems, such as the Fusion UV CuringSystems F-300 B [Fusion UV Curing Systems, Buffalo Grove, Ill.], HanoviaUV Curing System [Hanovia Corp., Newark, N.J.] and RC-500 A Pulsed UVCuring System [Xenon Corp., Woburn, Mass.], are well-suited toaccomplish the transformation. Also, a Sunlighter UW chamber fitted withlow intensity mercury vapor lamps and a turntable may accomplish thetransformation.

The required amount of energy may be delivered by exposing theelectrochromic monomer composition to a less powerful source ofelectromagnetic radiation for a longer period of time, through forexample multiple passes, or conversely, by exposing it to a morepowerful source of electromagnetic radiation for a shorter period oftime. In addition, each of those multiple passes may occur with a sourceat different energy intensities. In any event, those of ordinary skillin the art should choose an appropriate source of electromagneticradiation depending on the particular electrochromic monomercomposition, and place that source at a suitable distance therefromwhich, together with the length of exposure, optimizes thetransformation process. Generally, a slower, controlled cure, such asthat achieved by multiple passes using a less intense energy source, maybe preferable over a rapid cure using a more intense energy source, forexample, to minimize shrinkage during the transformation process. Also,it is desirable to use a source of electromagnetic radiation that isdelivered in an intermittent fashion, such as by pulsing or strobing, soas to ensure a thorough and complete cure without causing excessive heatbuild-up.

In transforming electrochromic monomer compositions into polychromicsolid films, shrinkage may be observed during and after thetransformation process of the electrochromic monomer composition into apolychromic solid film. This undesirable event may be controlled orlessened to a large extent by making appropriate choices among thecomponents of the electrochromic monomer composition. For instance,appropriately chosen polyfunctional monomers or cross-linking agents mayenhance resistance to shrinkage during the transformation process. Inaddition, a conscious control of the type and amount of plasticizer usedin the electrochromic monomer composition may also tend to enhanceresistance to shrinkage. While shrinkage may also be observed withpolychromic solid films that have been subjected to environmentalconditions, especially conditions of environmental accelerated aging,such as thermal cycling and low temperature soak, a conscious choice ofcomponents used in the electrochromic monomer composition may tend tominimize this event as well. In general, shrinkage may be decreased asthe molecular weight of the monomer employed is increased, and by usingindex matched inert fillers, such as glass beads or fibres.

Electrochromic devices may be manufactured with polychromic solid filmsof a particular thickness by preparing partially-cured polychromic solidfilms between the glass substrates of electrochromic assemblies withspacers or a thermoplastic spacing means having been placed on one orboth of the substrates. This partially-cured polychromic solid filmshould have a thickness slightly greater than that which the resultingpolychromic solid film will desirably assume in the completed device.The electrochromic assemblies should then be subjected to compression,such as that provided by an autoclave/vacuum bagging process, andthereafter be exposed to electromagnetic radiation to complete thetransformation into a polychromic solid film with the desired filmthickness.

FIGS. 1 and 2 show an electrochromic device assembled from thepolychromic solid films of the present invention. The electrochromicassembly 1 includes two substantially planar substrates 2, 3 positionedsubstantially parallel to one another. It is preferable that thesesubstrates 2, 3 be positioned as close to parallel to one another aspossible so as to avoid double imaging, which is particularly noticeablein mirrors, especially when the electrochromic media--i.e., thepolychromic solid film--is colored to a dimmed state.

A source of an applied potential need be introduced to theelectrochromic assembly 1 so that polychromic solid film 6 may color ina rapid, intense and uniform manner. That source may be connected byelectrical leads 8 to conducting strips, such as bus bars 7. The busbars 7 may be constructed of a metal, such as copper, stainless steel,aluminum or solder, or of conductive frits and epoxides, and should beaffixed to a conductive coating 4, coated on a surface of each of thesubstrates 2, 3. An exposed portion of the conductive coating 4 shouldbe provided for the bus bars 7 to adhere by the displacement of thecoated substrates 2, 3 in opposite directions relative to eachother--lateral from, but parallel to--, with polychromic solid film 6positioned between, and in abutting relationship with, the conductivesurface of the two substrates.

As noted above, coated on a surface of each of these substrates 2, 3 isa substantially transparent conductive coating 4. The conductive coating4 is generally from about 300 Å to about 10,000 Å in thickness, having arefractive index in the range of about 1.6 to about 2.2. Preferably, aconductive coating 4 with a thickness of about 1,200 Å to about 2,300 Å,having a refractive index of about 1.7 to about 1.9, is chosen dependingon the desired appearance of the substrate when the polychromic solidfilm situated therebetween is colored.

The conductive coating 4 should also be highly and uniformly conductivein each direction to provide a substantially uniform response as to filmcoloring once a potential is applied. The sheet resistance of thesetransparent conductive substrates 2, 3 may be below about 100 ohms persquare, with about 6 ohms per square to about 20 ohms per square beingpreferred. Such substrates 2, 3 may be selected from among thosecommercially available as glass substrates, coated with indium tin oxide("ITO") from Donnelly Corporation, Holland, Mich., or tin oxide-coatedglass substrates sold by the LOF Glass division of Libbey-Owens-FordCo., Toledo, Ohio under the tradename of "TEC-Glass" products, such as"TEC 10" (10 ohms per square sheet resistance), "TEC 12" (12 ohms persquare sheet resistance) and "TEC 20" (20 ohms per square sheetresistance) tin oxide-coated glass. Moreover, tin oxide coated glasssubstrates, commercially available from Pittsburgh Plate GlassIndustries, Pittsburgh, Pa. under the "SUNGATE" tradename, may beadvantageously employed herein. Also, substantially transparentconductive coated flexible substrates, such as ITO deposited ontosubstantially clear or tinted "MYLAR", may be used. Such flexiblesubstrates are commercially available from Southwall Corp., Palo Alto,Calif.

The conductive coating 4 coated on each of the substrates 2, 3 may beconstructed from the same material or different materials, including tinoxide, ITO, ITO-FW, ITO-HW, ITO-HWG, doped tin oxide, such asantimony-doped tin oxide and fluorine-doped tin oxide, doped zinc oxide,such as antimony-doped zinc oxide and aluminum-doped zinc oxide, withITO being preferred.

The substantially transparent conductive coated substrates 2, 3 may beof the full-wave length-type ("FW") (about 6 ohms per square to about 8ohms per square sheet resistance), the half-wave length-type ("HW")(about 12 ohms per square to about 15 ohms per square sheet resistance)or the half-wave length green-type ("HWG") (about 12 ohms per square toabout 15 ohms per square sheet resistance). The thickness of FW is about3,000 Å in thickness, HW is about 1,500 Å in thickness and HWG is about1,960 Å in thickness, bearing in mind that these substantiallytransparent conductive coated substrates 2, 3 may vary as much as about100 to about 200 Å. HWG has a refractive index of about 1.7 to about1.8, and has an optical thickness of about five-eighths wave to abouttwo-thirds wave. HWG is generally chosen for electrochromic devices,especially reflective devices, such as mirrors, whose desired appearancehas a greenish hue in color when a potential is applied.

Optionally, and for some applications desireably, the spaced-apartsubstantially transparent conductive coated substrates 2, 3 may have aweather barrier 5 placed therebetween or therearound. The use of aweather barrier 5 in the electrochromic devices of the present inventionis for the purpose of preventing environmental contaminants fromentering the device during long-term use under harsh environmentalconditions rather than to prevent escape of electrochromic media, suchas with an electrochemichromic device. Weather barrier 5 may be madefrom many known materials, with epoxy resins coupled with spacers,plasticized polyvinyl butyral (available commercially under the "SAFLEX"tradename from Monsanto Co., St. Louis, Mo.), ionomer resins (availablecommercially under the "SURLYN" tradename from E. I. du Pont de Nemoursand Co., Wilmington, Del.) and "KAPTON" high temperature polyamide tape(available commercially from E. I. du Pont de Nemours and Co.,Wilmington, Del.) being preferred. In general, it may be desireable touse within the electrochromic device, and particularly for weatherbarrier 5, materials such as nitrile containing polymers and butylrubbers that form a good barrier against oxygen permeation fromenvironmental exposure.

In the sandwich lamination technique, see supra, it is the thickness ofthe polychromic solid film itself, especially when a highly viscouselectrochromic monomer composition is used, optionally coupled witheither spacers or a thermoplastic spacing means, assembled within theelectrochromic devices of the present invention that determines theinterpane distance of the spaced-apart relationship at which thesubstrates are positioned. This interpane distance may be influenced bythe addition of spacers to the electrochromic monomer composition, whichspacers, when added to an electrochromic monomer composition, assist indefining the film thickness of the resulting polychromic solid film.And, the thickness of the polychromic solid film may be about 10 μm toabout 1000 μm, with about 20 μm to about 200 μm being preferred, a filmthickness of about 37 μm to about 74 μm being particularly preferred,and a film thickness of about 53 μm being most preferred depending ofcourse on the chosen electrochromic monomer composition and the intendedapplication.

By taking appropriate measures, electrochromic devices manufactured withpolychromic solid films may operate so that, upon application of apotential thereto, only selected portions of the device--i.e., throughthe polychromic solid film--will color in preference to the remainingportions of the device. In such segmented electrochromic devices, linesmay be scored or etched onto the conductive surface of either one orboth of substrates 2, 3, in linear alignment so as to cause a break inelectrical continuity between regions immediately adjacent to the break,by means such as chemical etching, mechanical scribing, laser etching,sand blasting and other equivalent means. By so doing, an addressablepixel may be created by the break of electrical continuity when apotential is applied to a pre-determined portion of the electrochromicdevice. The electrochromic device colors in only that pre-determinedportion demonstrating utility, for example, as an electrochromic mirror,where only a selected portion of the mirror advantageously colors toassist in reducing locally reflected glare or as an electrochromicinformation display device.

To prepare an electrochromic device containing a polychromic solid film,the electrochromic monomer composition may be dispensed onto theconductive surface of one of the substrates 2 or 3. The conductivesurface of the other substrate may then be placed thereover so that theelectrochromic monomer composition is dispersed uniformly onto andbetween the conductive surface of substrates 2, 3.

This assembly may then be exposed, either in a continuous orintermittent manner, to electromagnetic radiation, such as ultravioletradiation in the region between about 200 nm to about 400 nm for aperiod of about 2 seconds to about 10 seconds, so that theelectrochromic monomer composition is transformed by in situ curing intopolychromic solid film 6. The intermittent manner may include multipleexposures to such energy.

Once the electrochromic device is assembled with polychromic solid film6, a potential may be applied to the bus bars 7 in order to induce filmcoloring. The applied potential may be supplied from a variety ofsources including, but not limited to, any source of alternating current("AC") or direct current ("DC") known in the art, provided that, if anAC source is chosen, control elements, such as diodes, should be placedbetween the source and each of the conductive coatings 4 to ensure thatthe potential difference between the conductive coatings 4 does notchange polarity with variations in polarity of the applied potentialfrom the source. Suitable DC sources are storage batteries, solarthermal cells, photovoltaic cells or photoelectrochemical cells.

An electrochromic device, such as an electrochromic shade band where agradient opacity panel may be constructed by positioning the bus bars 7along the edges of the substrates in such a way so that only aportion--e.g., the same portion--of each of the substrates 2, 3 have thebus bars 7 affixed thereto. Thus, where the bus bars 7 are aligned withone another on opposite substrates 2, 3, the introduction of an appliedpotential to the electrochromic device will cause intense color to beobserved in only that region of the device onto which an electric fieldhas been created--i.e., only that region of the device having the busbars 7 so aligned. A portion of the remaining bleached region will alsoexhibit color extending from the intensely colored region at the busbar/non-bus bar transition gradually dissipating into the remainingbleached region of the device.

The applied potential generated from any of these sources may beintroduced to the polychromic solid film of the electrochromic device inthe range of about 0.001 volts to about 5.0 volts. Typically, however, apotential of about 0.2 volts to about 2.0 volts is preferred, with about1 volt to about 1.5 volts particularly preferred, to permit the currentto flow across and color the polychromic solid film 6 so as to lessenthe amount of light transmitted therethrough. The extent ofcoloring--i.e., high transmittance, low transmittance and intermediatetransmittance levels--at steady state in a particular device will oftendepend on the potential difference between the conductive surface of thesubstrates 2, 3, which relationship permits the electrochromic devicesof the present invention to be used as "gray-scale" devices, as thatterm is used by those of ordinary skill in the art.

A zero potential or a potential of negative polarity (i.e., a bleachingpotential) may be applied to the bus bars 7 in order to induce highlight transmittance through polychromic solid film 6. A zero potentialto about -0.2 volts will typically provide an acceptable response timefor bleaching; nevertheless, increasing the magnitude of the negativepotential to about -0.7 volts will often enhance response times. And, afurther increase in the magnitude of that potential to about -0.8 voltsto about -0.9 volts, or a magnitude of even more negative polarity asthe art-skilled should readily appreciate, may permit polychromic solidfilm 6 to form a light-colored tint while colored to a partial- orfully-dimmed state.

In electrochromic devices where the polychromic solid film is formedwithin the assembly by exposure to electromagnetic radiation, theperformance of the device may be enhanced by applying the positivepolarity of the potential to the substrate that faced theelectromagnetic radiation during the transformation process. Thus, inthe case of electrochromic mirrors manufactured in such a manner, thepositive polarity of the potential should be applied to the conductivesurface of the clear, front glass substrate, and the negative polarityof the potential applied to the conductive surface of the silvered, rearglass substrate, to observe such a beneficial effect.

In the context of an electrochromic mirror assembly, a reflectivecoating, having a thickness in the range of 250 Å to about 2,000 Å,preferably about 1,000 Å, should thereafter be applied to one of thetransparent conductive coated glass substrates 2 or 3 in order to form amirror. Suitable materials for this layer are aluminum, palladium,platinum, titanium, gold, chromium, silver and stainless steel, withsilver being preferred. As an alternative to such metal reflectors,multi-coated thin film stacks of dielectric materials or a high indexsingle dielectric thin film coating may be used as a reflector.Alternatively, one of the conductive coatings 4 may be a metallicreflective layer which serves not only as an electrode, but also as amirror.

It is clear from the teaching herein that should a window, sun roof orthe like be desirably constructed, the reflective coating need only beomitted from the assembly so that the light which is transmitted throughthe transparent panel is not further assisted in reflecting backtherethrough.

Similarly, an electrochromic optically attenuating contrast filter maybe manufactured in the manner described above, optionally incorporatinginto the electrochromic assembly an anti-reflective means, such as acoating, on the front surface of the outermost substrate as viewed by anobserver (see e.g., Lynam V); an anti-static means, such as a conductivecoating, particularly a transparent conductive coating of ITO, tin oxideand the like; index matching means to reduce internal and interfacialreflections, such as thin films of an appropriately selected opticalpath length; and/or light absorbing glass, such as glass tinted to aneutral density, such as "GRAYLITE" gray tinted glass (commerciallyavailable from Pittsburgh Plate Glass Industries, Pittsburgh, Pa.) and"SUNGLAS" Gray gray tinted glass (commercially available from Ford GlassCo., Detroit, Mich.), to augment contrast enhancement. Moreover, polymerinterlayers, which may be tinted gray, such as those used inelectrochromic constructions as described in Lynam III, may beincorporated into such electrochromic optically attenuating contrastfilters.

Electrochromic optical attenuating contrast filters may be an integralpart of a device or may be affixed to an already constructed device,such as cathode ray tube monitors. For instance, an optical attenuatingcontrast filter may be manufactured from a polychromic solid film andthen affixed, using a suitable optical adhesive, to a device that shouldbenefit from the properties and characteristics exhibited by thepolychromic solid film. Such optical adhesives maximize optical qualityand optical matching, and minimize interfacial reflection, and includeplasticized polyvinyl butyral, various silicones, polyurethanes such as"NORLAND NOA 65" and "NORLAND NOA 68", and acrylics such as "DYMAXLIGHT-WELD 478". In such contrast filters, the electrochromic compoundsare chosen for use in the polychromic solid film so that theelectrochromic assembly may color to a suitable level upon theintroduction of an applied potential thereto, and no undesirablespectral bias is exhibited. Preferably, the polychromic solid filmshould dim through a substantially neutral colored partial transmissionstate to a substantially neutral colored full transmission state.

Polychromic solid films may be used in electrochromic devices,particularly glazings and mirrors, whose functional surface issubstantially planar or flat, or that are curved with a convexcurvature, a compound curvature, a multi-radius curvature, a sphericalcurvature, an aspheric curvature, or combinations of such curvature. Forexample, flat electrochromic automotive mirrors may be manufacturedusing the polychromic solid films of the present invention. Also, convexelectrochromic automotive mirrors may be manufactured, with radii ofcurvature typically in the range of about 25" to about 250", preferablyin the range of about 35" to about 100", as are conventionally known. Inaddition, multi-radius automotive mirrors, such as those described inU.S. Pat. No. 4,449,786 (McCord), may be manufactured using thepolychromic solid films of the present invention. Multi-radiusautomotive mirrors may be used typically on the driver-side exterior ofan automobile to extend the driver's field of view and to enable thedriver to safely see rearward and to avoid blind-spots in the rearwardfield of view. Generally, such mirrors comprise a higher radius (evenflat) region closer to the driver and a lower radius (i.e., more curved)region outboard from the driver that serves principally as theblind-spot detection zone in the mirror. Indeed, such polychromic solidfilm-containing electrochromic multi-radius automotive mirrors maybenefit from the prolonged coloration performance of polychromic solidfilms and/or from the ability to address individual segments in suchmirrors.

Often, a demarcation means, such as a silk-screened or otherwise appliedline of black epoxy, may be used to separate the more curved, outboardblind-spot region from the less curved, inboard region of such mirrors.The demarcation means may also include an etching of a deletion line oran otherwise established break in the electrical continuity of thetransparent conductors used in such mirrors so that either one or bothregions may be individually or mutually addressed. Optionally, thisdeletion line may itself be colored black. Thus, the outboard, morecurved region may operate independently from the inboard, less curvedregion to provide an electrochromic mirror that operates in a segmentedarrangement. Upon the introduction of an applied potential, either ofsuch regions may color to a dimmed intermediate reflectance level,independent of the other region, or, if desired, both regions mayoperate together in tandem.

An insulating demarcation means, such as demarcation lines, dots and/orspots, may be placed within electrochromic devices, such as mirrors,glazings, optically attenuating contrast filters and the like, to assistin creating the interpane distance of the device and to enhance overallperformance, in particular the uniformity of coloration across largearea devices. Such insulating demarcation means, constructed from, forexample, epoxy coupled with glass spacer beads, plastic tape or die cutfrom plastic tape, may be placed onto the conductive surface of one ormore substrates by silk-screening or other suitable technique prior toassembling the device. The insulating demarcation means may begeometrically positioned across the panel, such as in a series ofparallel, uniformly spaced-apart lines, and may be clear, opaque, tintedor colorless and appropriate combinations thereof, so as to appeal tothe automotive stylist.

If the interpane distance between the substrates is to be, for example,about 250 μm, then the insulating demarcation means (being substantiallynon-deformable) may be screened, contacted or adhered to the conductivesurface of a substrate at a lesser thickness, for example, about 150 μmto about 225 μm. Of course, if substantially deformable materials areused as such demarcation means, a greater thickness, for example, about275 μm to about 325 μm, may be appropriate as well. Alternatively, theinsulating demarcation means may have a thickness about equal to that ofthe interpane distance of the device, and actually assist in bondingtogether the two substrates of the device.

In any event, the insulating demarcation means should prevent theconductive surfaces of the two substrates (facing one another in theassembled device) from contacting locally one another to avoidshort-circuiting the electrochromic system. Similarly, should theelectrochromic device be touched, pushed, impacted and the like at someposition, the insulating demarcation means, present within the interpanedistance between the substrates, should prevent one of the conductivesurfaces from touching, and thereby short-circuiting, the otherconductive surface. This may be particularly advantageous when flexiblesubstrates, such as ITO-coated "MYLAR", are used in the electrochromicdevice.

Although spacers may be added to the electrochromic monomer compositionand/or distributed across the conductive surface of one of thesubstrates prior to assembling the device, such random distributionprovides a degree of uncertainty as to their ultimate location withinthe electrochromic device. By using such a screen-on technique asdescribed above, a more defined and predictable layout of the insulatingdemarcation means may be achieved.

Using such insulating demarcation means, one or both of the substrates,either prior to or after assembly in the device, may be divided intoseparate regions with openings or voids within the insulatingdemarcation means interconnecting adjacent regions so as to permit aready introduction of the electrochromic monomer composition into theassembly.

A demarcation means may be used that is conductive as well, providedthat it is of a smaller thickness than the interpane distance and/or alayer of an insulating material, such as a non-conductive epoxy,urethane or acrylic, is applied thereover so as to prevent conductivesurfaces from contacting one another and thus short-circuiting theelectrochromic assembly. Such conductive demarcation means includeconductive frits, such as silver frits like the #7713 silver conductivefrit available commercially from E. I. de Pont de Nemours and Co.,Wilmington, Del., conductive paint or ink and/or metal films, such asthose disclosed in Lynam IV. Use of a conductive demarcation means, suchas a line of the #7713 silver conductive frit, having a width of about0.09375" and a thickness of about 50 μm, placed on the conductivesurface of one of the substrates of the electrochromic device mayprovide the added benefit of enhancing electrochromic performance byreducing bus bar-to-bus bar overall resistance and thus enhancinguniformity of coloration, as well as rapidity of response, particularlyover large area devices.

Once constructed, any of the electrochromic devices described herein mayhave a molded casing placed therearound. This molded casing may bepre-formed and then placed about the periphery of the assembly or, forthat matter, injection molded therearound using conventional techniques,including injection molding of thermoplastic materials, such aspolyvinyl chloride [see e.g., U.S. Pat. No. 4,139,234 (Morgan)], orreaction injection molding of thermosetting materials, such aspolyurethane or other thermosets [see e.g., U.S. Pat. No. 4,561,625(Weaver)]. Thus, modular automotive glazings incorporating polychromicsolid films may be manufactured.

Each of the documents cited in the present teaching is hereinincorporated by reference to the same extent as if each document hadindividually been incorporated by reference.

In view of the above description of the instant invention, it is evidentthat a wide range of practical opportunities is provided by the teachingherein. The following examples illustrate the benefits and utility ofthe present invention and are provided only for purposes ofillustration, and are not to be construed so as to limit in any way theteaching herein.

EXAMPLES

In each of these examples, we selected random assemblies, fractured thesubstrates of the assemblies and scraped the polychromic solid film thathad formed during the transformation process within the assembly fromthe broken substrate.

Scatter Safety Aspect of Electrochromic Devices Manufactured withPolychromic Solid Films

To demonstrate the safety performance of the electrochromic devicesmanufactured according to the these examples, we simulated the impact ofan accident by impacting the glass substrates of randomly selecteddevices with a solid object so as to shatter the glass substrates ofthose devices. We observed that in each instance the shattered glass washeld in place by the polychromic solid film such that glass shards fromthe broken substrates did not separate and scatter from the device.

Stability and Cyclability of Electrochromic Devices Manufactured withPolychromic Solid Films

In general, we observed good cycle stability, heat stability,performance under prolonged coloration and ultraviolet stability of theelectrochromic devices manufactured with the polychromic solid films ofthe present invention.

To demonstrate the cycle stability, ultraviolet stability and thermalstability of some of the electrochromic devices manufactured with thepolychromic solid films of the present invention, we subjectedelectrochromic mirrors to (1) 15 seconds color--15 seconds bleach cyclesat both room temperature and about 50° C.; (2) ultraviolet stabilitytests by exposing the electrochromic mirrors to at least about 900 KJ/m²using a Xenon Weatherometer as per SAE J1960 and (3) thermal stabilitytests at about 85° C.

In these mirrors, we observed no change of electrochromic performance ordegrading of the electrochromic devices after more than about 100,000cycles (15 seconds color--15 seconds bleach) at room temperature andmore than about 85,000 cycles (15 seconds color--15 seconds bleach) atabout 50° C., and after exposure to about 900 KJ/m² of ultravioletradiation and to about 85° C. for about 360 hours indicating excellentcycle stability and weatherability.

Example 1

In this example, we chose a RMPT-HVBF₄ electrochromic pair, inconjunction with a commercially available ultraviolet curableformulation, to illustrate the beneficial properties and characteristicsof the polychromic solid films and electrochromic interior automotivemirrors manufactured therewith.

A. Synthesis and Isolation of RMPT

We synthesized 2-methyl-phenothiazin-3-one according to the proceduredescribed in European Patent Publication EP 0 115 394 (Merck FrosstCanada). To reduce MPT to RMPT, we followed the redox proceduredescribed in commonly assigned co-pending U.S. patent application Ser.No. 07/935,784 (filed Aug. 27, 1992).

B. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.7% HVBF₄ (as a cathodic compound),about 1.6% RMPT (as an anodic compound), both homogeneously dispersed ina combination of about 47.4% propylene carbonate (as the plasticizer)and, as a monomer component, about 52.6% "IMPRUV" (an ultravioletcurable formulation). We thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

C. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HW-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×37 μm, with aweather barrier of an epoxy resin coupled with spacers of about 37 μmalso applied.

We placed into the mirror assemblies the electrochromic monomercomposition of Example 1(B), supra, by the vacuum backfilling technique[as described in Varaprasad III, supra].

D. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 1(B), supra, wasuniformly applied within the mirror assemblies of Example 1(C), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B. While the belt advanced initially at a rate of abouttwenty-five feet per minute, we exposed the assemblies to ultravioletradiation generated by the D fusion lamp of the F-300 B. We passed theassemblies under the fusion lamp light eight times at that rate, pausingmomentarily between passes to allow the assemblies to cool, then eighttimes at a rate of about fifteen feet per minute again pausingmomentarily between passes to allow the assemblies to cool and finallythree times at a rate of about ten feet per minute with theaforementioned pausing between passes.

E. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a bluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71% reflectance which decreased to a lowreflectance of about 10.8% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 3.7 seconds. We madethis determination by following the SAE J964A standard procedure of theSociety of Automotive Engineers, with a reflectometer--set inreflectance mode--equipped with a light source (known in the art asIlluminant A) and a photopic detector assembly interfaced with a dataacquisition system.

We also observed that the mirror bleached from about 20% reflectance toabout 60% reflectance in a response time of about 7.1 seconds underabout a zero applied potential. We noted the bleaching to be uniform,and the bleached appearance to be silvery.

Example 2

In this example, we chose a RMPT-HVBF₄ electrochromic pair, inconjunction with a combination of commercially available ultravioletcurable formulations, to illustrate the beneficial properties andcharacteristics of the polychromic solid film and the electrochromicinterior automotive mirrors manufactured therewith by using the sandwichlamination technique.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.6% HVBF₄ (as a cathodic compound), about 1.2% RMPT (as an anodiccompound), both homogeneously dispersed in a combination of about 40%propylene carbonate (as a plasticizer) and, in combination as a monomercomponent, about 50% "QUICK CURE" B-565 (an acrylatedurethane/ultraviolet curable formulation) and about 10% "ENVIBAR" UV1244 (a cycloalkyl epoxide/ultraviolet curable formulation). Wethoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

In this example, we assembled interior automotive mirrors by dispensinga portion of the electrochromic monomer composition of Example 2(A),supra, onto the conductive surface of a tin oxide-coated glass substrate(the other surface of the substrate being silver-coated so as to form amirror) onto which we also placed 37 μm glass beads, and then positionedthereover the conductive surface of a clear, tin oxide-coated glasssubstrate. These glass substrates, commercially available under thetrade name "TEC-Glass" products as "TEC-20" from Libbey-Owens-Ford Co.,Toledo, Ohio, having dimensions of about 3"×6", were assembled to forman interpane distance between the glass substrates of about 37 μm. Inthis way, the electrochromic monomer composition was located between theconductive surface of the two glass substrates of the mirror assemblies.

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 2(A), supra, wasuniformly applied within the mirror assemblies of Example 2(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B. While the belt advanced initially at a rate of abouttwenty feet per minute, we exposed the assemblies to ultravioletradiation generated by the D fusion lamp of the F-300 B. We passed theassemblies under the fusion lamp light twelve times at that rate,pausing between every third or fourth pass to allow the assemblies tocool.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.3 volts to one of the mirrors, andthereafter observed that the mirror colored rapidly and uniformly to abluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 57% reflectance which decreased to a lowreflectance of about 9.3%. The response time for the reflectance tochange from about 55% to about 20% was about 10 seconds when a potentialof about 1.3 volts was applied thereto. We made this determination bythe reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 50% reflectance in a response time of about 56 seconds under aboutzero applied potential. We noted the bleaching to be uniform, and thebleached appearance to be silvery.

Example 3

In this example, we compared the beneficial properties andcharacteristics of a polychromic solid film prepared using ferrocene asan anodic electrochromic compound, and manufactured within an exteriorautomotive mirror [Example 3(B)(1) and (D)(1), infra] and interiorautomotive mirrors [Example 3(B)(2) and (D)(2), infra]. We alsoinstalled an interior automotive mirror as a rearview mirror in anautomobile to observe its performance under conditions attendant withactual automotive use.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.4% EVClO₄ (as a cathodic compound), about 2% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising, in combination as the plasticizer component, about 48.6%propylene carbonate and about 8.8% cyanoethyl sucrose and, incombination as a monomer component, about 17.7% caprolactone acrylateand about 13.3% polyethylene glycol diacrylate (400). We also addedabout 0.9% benzoin i-butyl ether (as a photoinitiator) and about 4.4%"UVINUL" N 35 (as an ultraviolet stabilizing agent), and thoroughlymixed this electrochromic monomer composition to ensure that ahomogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

1. Exterior Automotive Mirror

We assembled exterior automotive mirrors from HW-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 3.5"×5.5"×74 μm, with aweather barrier of an epoxy resin coupled with spacers of about 74 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 3(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

2. Interior Automotive Mirror

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×44 μm, with aweather barrier of an epoxy resin coupled with spacers of about 44 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 3(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 3(A), supra, wasuniformly applied within each of the respective mirror assemblies ofExample 3(B)(1) and (2), supra, we placed the assemblies onto theconveyor belt of a Fusion UV Curing System F-300 B, and exposed theassemblies to ultraviolet radiation in the same manner as described inExample 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors of Example 3(B), supra, and to two of the electrochromic mirrorsof Example 3(C), supra. Our observations follow.

1. Exterior Automotive Mirror

We observed that the electrochromic mirror colored rapidly and uniformlyto a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the exterior mirror decreased from about 80.5% to about 5.7%, with achange in the reflectance of about 70% to about 20% in a response timeof about 5.0 seconds when a potential of about 1.3 volts was appliedthereto. We made this determination by the reflectometer described inExample 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 9.2 seconds, underabout a zero applied potential. We noted the bleaching to be uniform,and the bleached appearance to be silvery.

2. Interior Automotive Mirror

We observed that each of a first and second electrochromic mirrorcolored rapidly and uniformly to a blue color with a greenish hue.

In addition, we observed that for the first mirror the high reflectanceat the center portion of the interior mirror decreased from about 80.2%to about 6.3%, with a change in the reflectance of about 70% to about20% in a response time of about 3.1 seconds when a potential of about1.3 volts was applied thereto. The second mirror exhibited comparableresults, with the reflectance decreasing from about 78.4% to about 7.5%in about 2.7 seconds. We made these determinations by the reflectometerdescribed in Example 1, supra.

We also observed that the first mirror bleached from about 10%reflectance to about 60% reflectance in a response time of about 3.9seconds under about a zero applied potential, and the second mirrorbleached to the same extent in about 3.6 seconds. We noted the bleachingto be uniform, and the bleached appearance to be silvery.

We have successfully installed and operated such an electrochromicmirror in an automobile as a rearview mirror and achieved excellentresults.

Example 4

In this example, we chose t-butyl ferrocene as the anodic electrochromiccompound together with a monomer component containing the combination ofa monomer and a commercially available ultraviolet curable formulationto illustrate the beneficial properties and characteristics of thepolychromic solid films made therefrom and the electrochromic interiorautomotive mirrors manufactured therewith.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.9% EVClO₄ (as a cathodic compound), about 2.3% t-butyl ferrocene(as an anodic compound), both homogeneously dispersed in a combinationcomprising about 61.7% propylene carbonate (as a plasticizer) and, incombination as a monomer component, about 10.7% caprolactone acrylateand about 10.6% "SARBOX" acrylate resin (SB 500) (an ultraviolet curableformulation). We also added about 1.3% "IRGACURE" 184 (as aphotoinitiator) and about 4.4% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 4(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 4(A), supra, wasuniformly applied within the mirror assemblies of Example 4(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors of Example 4(B) and (C), supra, and observed this mirror tocolor rapidly and uniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 79.3% reflectance which decreased to a lowreflectance of about 9.8% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.3 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 3.0 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Examples 5 Through 8

In Examples 5 through 8, we compared the beneficial properties andcharacteristics of polychromic solid films prepared from ferrocene, andthree alkyl derivatives thereof, as the anodic electrochromic compoundand manufactured within interior automotive mirrors.

Example 5

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 2.1% dimethyl ferrocene (as an anodic compound), bothhomogeneously dispersed in a combination of about 51.5% propylenecarbonate (as a plasticizer) and about 34.3% "QUICK CURE" B-565 (as amonomer component). We also added about 8.6% "UVINUL" N 35 (as anultraviolet stabilizing agent), and thoroughly mixed this electrochromicmonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×1×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 5(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 5(A), supra, wasuniformly applied within the mirror assemblies of Example 5(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UW CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71.9% reflectance which decreased to a lowreflectance of about 7.5% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.2 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 6

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 2.3% n-butyl ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 51.3% propylene carbonate (as aplasticizer) and about 34.3% "QUICK CURE" B-565 (as a monomercomponent). We also added about 8.6% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied. We placed into these mirror assemblies the electrochromicmonomer composition of Example 6(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 6(A), supra, wasuniformly applied within the mirror assemblies of Example 6(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.8% reflectance which decreased to a lowreflectance of about 7.8% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.5 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.3 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 7

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 2.3% t-butyl ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 51.3% propylene carbonate (as aplasticizer) and about 34.3% "QUICK CURE" B-565 (as a monomercomponent). We also added about 8.6% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5"×10"×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 7(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition as of Example 7(A), supra,was uniformly applied within the mirror assemblies of Example 7(B),supra, we placed the assemblies onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assemblies to ultravioletradiation in the same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.1% reflectance which decreased to a lowreflectance of about 7.8% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.5 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.3 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 8

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 3.5% EVClO₄ (as a cathodic compound),about 1.8% ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 51.8% propylene carbonate (as aplasticizer) and about 34.3% "QUICK CURE" B-565 (as a monomercomponent). We also added about 8.6% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5"×10"×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 8(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 8(A), supra, wasuniformly applied within the mirror assemblies of Example 8(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.7% reflectance which decreased to a lowreflectance of about 7.9% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.7 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.8 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 9

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.9% EVClO₄ (as a cathodic compound), about 1.2% t-butyl ferroceneand about 1.0% DMPA (in combination as the anodic compound),homogeneously dispersed in a combination comprising about 45% propylenecarbonate, about 8.9% cyanoethyl sucrose and about 8.9%3-hydroxypropionitrile (in combination as a plasticizer component) and,in combination as a monomer component, about 17.7% caprolactoneacrylate, about 11.5% polyethylene glycol diacrylate (400) and about1.8% 1,6-hexanediol diacrylate. We also added about 0.9% "IRGACURE" 184(as a photoinitiator) and about 4.4% "UVINUL N 35" (as an ultravioletstabilizing agent), and we thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5"×10"×44 μm, with a weather barrierof an epoxy resin coupled with spacers of about 44 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 9(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 9(A), supra, wasuniformly applied within the mirror assemblies of Example 9(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed that the mirror colored rapidly anduniformly to a bluish green color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 78.2% decreased to a low reflectance of about8.2%, with a change in the reflectance of about 70% to about 20% in aresponse time of about 1.9 seconds when a potential of about 1.3 voltswas applied thereto. We made this determination by the reflectometerdescribed in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 5.4 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 10

In this example, like Example 2, we chose to illustrate the sandwichlamination technique of manufacturing electrochromic devices todemonstrate its efficiency in the context of the present invention.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.0% EVClO₄ (as a cathodic compound), about 1.9% t-butyl ferrocene(as an anodic compound), both homogeneously dispersed in a combinationof about 31.7% propylene carbonate (as a plasticizer), and, incombination as a monomer component, about 31.7% "QUICK CURE" B-565 andabout 31.7% Urethane Acrylate (Soft) (CN 953). We thoroughly mixed thiselectrochromic monomer composition to ensure that a homogenousdispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled rectangular mirrors by dispensing a portion of theelectrochromic monomer composition of Example 10(A), supra, onto theconductive surface of a silvered "TEC-20" glass substrate onto which wealso placed 150 μm glass beads, and then positioned thereover theconductive surface of a clear "TEC-20" glass substrate. We assembledthese glass substrates, having dimensions of about 5.5"×7", undermoderate pressure to form an interpane distance between the glasssubstrates of about 150 μm. In this way, the electrochromic monomercomposition was located between the conductive surfaces of the two glasssubstrates of the mirror assemblies.

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 10(A), supra, wasuniformly applied within the mirror assemblies of Example 10(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.3 volts to one of the electrochromicmirror, and thereafter observed that the mirror colored rapidly anduniformly to a greenish blue color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 66.7% reflectance which decreased to a lowreflectance of about 5.8%. The response time for the reflectance tochange from about 60% to about 5.9% was about 30 seconds when apotential of about 1.3 volts was applied thereto. We made thisdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 5.9% reflectance toabout 60% reflectance in a response time of about 180 seconds underabout zero applied potential.

Example 11

In this example, we chose to illustrate the beneficial properties andcharacteristics of the polychromic solid films manufactured withinelectrochromic glazings, that may be used as small area transmissivedevices, such as optical filters and the like.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.5% HVBF₄ (as a cathodic compound), about 1.1% MPT having beenpreviously reduced by contacting with zinc [see Varaprasad IV andcommonly assigned co-pending U.S. patent application Ser. No.07/935,784] (as an anodic compound), both homogeneously dispersed in acombination comprising, in combination as a plasticizer, about 47.7%propylene carbonate and about 1% acetic acid, and about 47.7% "QUICKCURE" B-565 (as a monomer component). We thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Glazing Assembly with Electrochromic Monomer Composition

We assembled electrochromic glazings from HW-ITO coated glass substrates(where the conductive surface of each glass substrate faced oneanother), with the glass having a sheet resistance of about 15 ohms persquare. The dimensions of the glazing assemblies were about 2.5"×10"×53μm, with a weather barrier of an epoxy resin coupled with spacers ofabout 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 11(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Glazingto Polychromic Solid Film

Once the electrochromic composition of Example 11(A), supra, wasuniformly applied within the glazing assemblies of Example 11(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Glazing

We applied a potential of about 1.3 volts to the electrochromic glazingsof Example 11(B) and (C), supra. We observed that the electrochromicglazings colored rapidly and uniformly to a bluish purple color.

In addition, we observed that the high transmission at the centerportion of the glazing decreased from about 79.2% to about 7.4%, with achanged transmission of about 70% to about 20% in a response time ofabout 4.4 seconds when a potential of about 1.3 volts was appliedthereto. We made this determination by the detection method described inExample 1, supra, except that the reflectometer was set in transmissionmode.

We also observed that the glazing bleached from about 15% transmissionto about 60% transmission in a response time of about 8.4 seconds, underabout a zero applied potential. We noted good cycle stability,ultraviolet stability and thermal stability.

Example 12

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.7% HVBF₄ (as a cathodic compound), about 1.6% RMPT (as an anodiccompound), both homogeneously dispersed in a combination comprisingabout 46.2% 3-hydroxypropionitrile (as a plasticizer), and, incombination as a monomer component, about 23.1%2-(2-ethoxyethoxy)-ethylacrylate and about 23.1% tetraethylene glycoldiacrylate. We also added about 2.3% "ESACURE" TZT (as aphotoinitiator), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled electrochromic mirrors from "TEC-20" glass substrates(where the conductive surface of each glass substrate faced oneanother), having dimensions of about 2.5"×10"×37 μm, with a weatherbarrier of an epoxy resin coupled with spacers of about 37 μm alsoapplied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 12(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 12(A), supra, wasuniformly applied within the mirror assemblies of Example 12(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors of Example 12(B) and (C), supra, and observed this mirror tocolor rapidly and uniformly to a bluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 68.4% reflectance which decreased to a lowreflectance of about 13.3% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 65% to about 20%when that potential was applied thereto was about 3.0 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 15% reflectance toabout 60% reflectance in a response time of about 3.0 seconds underabout a zero applied potential. We noted the bleaching to be uniform,and the bleached appearance to be silvery.

Example 13

In this example, we chose to illustrate the beneficial properties andcharacteristics of polychromic solid films manufactured withinelectrochromic glazings consisting of sun roofs using a compatibilizingplasticizer component. Also, in this example, we chose to formulate theelectrochromic monomer composition with an additional monomer havingpolyfunctionality as a compatibilizing agent for the polychromic solidfilm.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 4.0% HVBF₄ (as a cathodic compound),about 1.7% RMPT (as an anodic compound), both homogeneously dispersed ina combination comprising, in combination as a plasticizer, about 10.2%propylene carbonate, about 17% benzyl acetone and about 14.7% cyanoethylsucrose, and, in combination as a monomer component, about 33.5% "QUICKCURE" B-565 and about 18.9% polyethylene glycol diacrylate (400). Wethoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Glazing Assembly with Electrochromic Monomer Composition

We constructed a glazing assembly consisting of a sun roof model bydispensing a portion of the electrochromic monomer composition ofExample 13(A), supra, onto the conductive surface of a "TEC-10" glasssubstrate onto which we also placed 100 μm glass beads, and thenpositioned thereover another "TEC-10" glass substrate, so that theelectrochromic monomer composition was between and in contact with theconductive surface of the two glass substrates. We used "TEC-10" glasssubstrates having dimensions of about 6"×16.5", with bus bars attachedat the lengthwise side of the substrates to create a distancetherebetween of about 16.5". The interpane distance between the "TEC-10"glass substrates was about 100 μm.

C. Transformation of Electrochromic Monomer Composition within GlazingAssembly to Polychromic Solid Film

Once the electrochromic monomer composition of Example 13(A), supra, wasuniformly applied within the glazing assembly of Example 13(B), supra,we placed the assembly onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assembly to ultraviolet radiation in thesame manner as described in Example 2(C), supra.

D. Use of Electrochromic Glazing Assembly

We applied a potential of about 1.3 volts to the glazing assembly, andthereafter observed the assembly to color rapidly and uniformly to abluish purple color.

In addition, we observed that the high transmission at the centerportion of the glazing assembly was about 60.7% transmission whichdecreased to a low transmission of about 6.0% when about 1.3 volts wasapplied thereto. The response time for the transmission to change fromabout 60% to about 10% when that potential was applied thereto was about3.8 minutes. We made this determination by the detection methoddescribed in Example 1, supra, except that the reflectometer was set intransmission mode.

We also observed that the glazing assembly bleached from about 10%transmission to about 45% transmission in a response time of about 4.2minutes under about a zero applied potential.

Example 14

In this example, we chose to manufacture large area electrochromicmirrors, by the two hole filling technique, to demonstrate thebeneficial properties and characteristics of the polychromic solid filmswithin large truck mirrors.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 1.9% EVClO₄ (as a cathodic compound), about 1.2% RMPT (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 53.3% propylene carbonate (as a plasticizer) and about43.6% "QUICK CURE" B-565 (as a monomer component). We thoroughly mixedthis electrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled large truck mirrors from FW-ITO glass substrates (where theconductive surface of each glass substrate faced one another), with theclear, front glass and the silvered, rear glass having a sheetresistance of about 6 to about 8 ohms per square. The dimensions of themirror assemblies were about 6.5"×15"×44 μm, with a weather barrier ofan epoxy resin coupled with spacers of about 44 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 14(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 14(A), supra, wasuniformly applied within the truck mirror assemblies of Example 14(B),supra, we placed the assemblies onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assemblies to ultravioletradiation in the same manner as described in Example 2(C), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromictruck mirrors, and thereafter observed that the mirror colored rapidlyand uniformly to a bluish purple color.

In addition, we observed that the high reflectance at the center portionof the mirror was about 67.4% decreased to a low reflectance of about7.9%, with a changed reflectance of about 65% to about 20% in a responsetime of about 7.1 seconds when a potential of about 1.3 volts wasapplied thereto. We made this determination by the reflectometerdescribed in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 55% reflectance in a response time of about 15.0 seconds underabout a zero applied potential, and to its high reflectance shortlythereafter.

The electrochromic truck mirrors performed satisfactorily with its longaxis positioned in vertical alignment with the ground.

Example 15

In this example, we have illustrated that the electrochromic monomercomposition may be prepared in stages and thereafter used to manufacturepolychromic solid films, and electrochromic devices manufactured withsame, that demonstrates the beneficial properties and characteristicsherein described. Also, in this example, like Examples 12 and 13, supra,we chose to formulate the electrochromic monomer composition with adifunctional monomer component to illustrate the properties andcharacteristics attendant with the addition of that component.

A. Preparation of Electrochromic Monomer Composition

The electrochromic monomer composition of this example comprised byweight about 3.9% EVClO₄ (as a cathodic compound), about 2.3% t-butylferrocene (as an anodic compound), both homogeneously dispersed in acombination of about 62% propylene carbonate (as the plasticizer), and,in combination as a monomer component, about 20% caprolactone acrylateand about 6.5% polyethylene glycol diacrylate (400). We also added about0.9% "IRGACURE" 184 (as a photoinitiator) and about 4.4% "UVINUL" N 35(as an ultraviolet stabilizing agent), and thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

We prepared the above composition by first combining the propylenecarbonate, caprolactone acrylate, polyethylene glycol diacrylate (400)and "IRGACURE" 184, with stirring and bubbling nitrogen gas through thecombination, and initiating cure by exposing this combination to asource of fluorescent light at room temperature for a period of time ofabout 10 minutes. At this point, we removed the source of fluorescentlight, and combined therewith the EVClO₄, t-butyl ferrocene and "UVINUL"N 35 to obtain a homogeneously dispersed electrochromic monomercomposition. We monitored the extent of cure by the increase ofviscosity.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5"×10"×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 15(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 15(A), supra, wasuniformly applied within the mirror assemblies of Example 15(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.3 volts to one of the mirrors, andthereafter observed that the mirror colored rapidly and uniformly to ablue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 82.6% reflectance which decreased to a lowreflectance of about 8.8%. The response time for the reflectance tochange from about 70% to about 20% was about 2.5 seconds at about roomtemperature and about the same when the surrounding temperature wasreduced to about -28° C. when a potential of about 1.3 volts was appliedthereto. We made that determination by the reflectometer described inExample 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 1.9 seconds at aboutroom temperature and of about 7.4 seconds when the surroundingtemperature was reduced to about -28° C. under about zero appliedpotential.

Example 16

In this example, we chose to manufacture the polychromic solid film froma commercially available epoxy resin together with a cross-linking agentto illustrate enhanced prolonged coloration performance attained whensuch combinations are used in the electrochromic monomer composition.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.7% HVBF₄ (as a cathodic compound), about 1.7% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 64.5% propylene carbonate (as a plasticizer) and about26.5% "CYRACURE" resin UVR-6105 (as a monomer component) and about 1.2%2-ethyl-2-(hydroxymethyl)-1,3-propanediol (as a cross-linking agent). Wealso added about 1.4% "CYRACURE" UVI-6990 (as a photoinitiator), andthoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors HWG-ITO coated glass substrates(where the conductive surface of each glass substrate faced oneanother), with the clear, front glass and silvered, rear glass having asheet resistance of about 15 ohms per square. The dimensions of themirror assemblies were about 2.5"×10"×53 μm, with a weather barrier ofan epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 16(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 16(A), supra, wasuniformly applied within the mirror assemblies of Example 16(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors prepared according to Examples 16(B) and (C), supra, andobserved this mirror to color rapidly and uniformly to a blue color witha greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 80.0% reflectance which decreased to a lowreflectance of about 7.3% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.9 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 3.8 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

We further observed that the mirror bleached uniformly andsatisfactorily after prolonged coloration in excess of about 8 hours.

Example 17

In this example, like Example 16, we chose to manufacture polychromicsolid films from a commercially available epoxy resin together with across-linking agent to illustrate enhanced prolonged colorationperformance attained when such combinations are used in theelectrochromic monomer composition.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 4.7% HVBF₄ (as a cathodic compound),about 1.4% ferrocene (as an anodic compound), both homogeneouslydispersed in a combination of about 64.6% propylene carbonate (as aplasticizer), about 17.5% "CYRACURE" resin UVR-6105 (as a monomercomponent) and about 10.1% "CARBOWAX" PEG 1450 (as a cross-linkingagent). We also added about 1.4% "CYRACURE" UVI-6990 (as aphotoinitiator), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.5"×10"×53 μm, with a weather barrierof an epoxy resin coupled with spacers of about 53 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 17(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 17(A), supra, wasuniformly applied within the mirror assemblies of Example 17(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to one of the electrochromicmirrors, and thereafter observed this mirror to color rapidly anduniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 75.2% reflectance which decreased to a lowreflectance of about 7.6% when about 1.3 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.2 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

We further observed that the mirror bleached uniformly andsatisfactorily after prolonged coloration in excess of about 8 hours.

Example 18

In this example, we chose ferrocene as the anodic electrochromiccompound together with a monomer component containing the combination ofa monofunctional monomer and a difunctional monomer to illustrate thebeneficial properties and characteristics of polychromic solid filmsmade therefrom.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.3% EVClO₄ (as a cathodic compound), about 1.9% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 55.9% propylene carbonate (as a plasticizer) and, incombination as a monomer component, about 12.7% caprolactone acrylateand about 17.2% polyethylene glycol diacrylate (400). We also addedabout 3.5% benzoin i-butyl ether (as a photoinitiator) and about 4.3%"UVINUL" N 35 (as an ultraviolet stabilizing agent), and thoroughlymixed this electrochromic monomer composition to ensure that ahomogenous dispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.51"×10"×44 μm, with aweather barrier of an epoxy resin coupled with spacers of about 44 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 18(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 18(A), supra, wasuniformly applied within the mirror assemblies of Example 18(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B. While the belt advanced initially at a rate of aboutfifty feet per minute, we exposed the assemblies to ultravioletradiation generated by the D fusion lamp of the F-300 B. We passed thesemirror assemblies under the fusion lamp fifteen times pausing for twominute intervals between every third pass, then nine times at that ratepausing for two minute intervals between every third pass, and finallysix times at a rate of about twenty-five feet per minute pausing for twominute intervals after every other pass.

D. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to one of the electrochromicmirrors of Examples 18(B) and (C), supra, and observed this mirror tocolor rapidly and uniformly to a blue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 77.1% reflectance which decreased to a lowreflectance of about 7.9% when about 1.5 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 2.8 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 2.6 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 19

In this example, we chose ferrocene as the anodic electrochromiccompound together with a monomer component containing the combination ofa monomer and a commercially available ultraviolet curable formulationto illustrate the beneficial properties and characteristics ofpolychromic solid films made therefrom.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.3% EVClO₄ (as a cathodic compound), about 1.9% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about55.9% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 10.3% caprolactone acrylate, about 15.5%polyethylene glycol diacrylate (400) and about 4.3% "SARBOX" acrylateresin (SB 500). We also added about 3.5% benzoin i-butyl ether (as aphotoinitiator) and about 4.3% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 19(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 19(A), supra, wasuniformly applied within the mirror assemblies of Example 19(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 18 (C), supra.

D. Use of Electrochromic Mirrors

We applied a potential of about 1.5 volts to one of the mirrors, andthereafter observed that the mirror colored rapidly and uniformly to ablue color with a greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 79.6% reflectance which decreased to a lowreflectance of about 7.6%. The response time for the reflectance tochange from about 70% to about 20% was about 2.2 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 2.5 seconds underabout zero applied potential.

Example 20

In this example, we chose to manufacture interior rearview mirrors frompolychromic solid films prepared with a commercially available epoxyresin together with a cross-linking agent to illustrate enhancedprolonged coloration performance attained when such combinations areused in the electrochromic monomer composition.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.6% EVClO₄ (as a cathodic compound), about 2.1% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 57.4% propylene carbonate (as a plasticizer) and, incombination as a monomer component, about 8.2% "CYRACURE" resin UVR-6105and about 14.0% caprolactone, and about 1.1%2-ethyl-2-(hydroxymethyl)-1,3-propanediol (as a cross-linking agent). Wealso added, in combination as photoinitiators, about 1.4% "CYRACURE"UVI-6990 and about 1.5% benzoin i-butyl ether, and thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors HWG-ITO coated glass substrates(where the conductive surface of each glass substrate faced oneanother), with the clear, front glass and the silvered, rear glasshaving a sheet resistance of about 15 ohms per square. The dimensions ofthe mirror assemblies were about 2.51"×10"×44 μm, with a weather barrierof an epoxy resin coupled with spacers of about 44 μm also applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 20(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 20(A), supra, wasuniformly applied within the mirror assemblies of Example 20(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.4 volts to one of the electrochromicmirrors prepared according to Examples 20(B) and (C), supra, andobserved this mirror to color rapidly and uniformly to a blue color witha greenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 76.9% reflectance which decreased to a lowreflectance of about 7.9% when about 1.4 volts was applied thereto. Theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto was about 3.1 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 3.3 seconds underabout a zero applied potential. We noted the bleaching to be uniform.

Example 21

In this example, we illustrate that a prolonged application of a bleachpotential--i.e., a potential having a polarity opposite to that used toachieve color--, having a magnitude greater than about 0.2 volts, andpreferably about 0.4 volts, may be used to enhance bleach speeds ofelectrochromic devices, such as automotive rearview mirrors,manufactured with polychromic solid films as the medium of variablereflectance.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.3% EVClO₄ (as a cathodic compound), about 1.9% ferrocene (as ananodic compound), both homogeneously dispersed in a combinationcomprising about 60.2% propylene carbonate (as a plasticizer) and, incombination as a monomer component, about 8.6% caprolactone acrylate,about 12.9% polyethylene glycol diacrylate (400) and about 4.3% "SARBOX"acrylate resin (SB 500). We also added about 3.4% "IRGACURE" 184 (as aphotoinitiator) and about 4.3% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled interior automotive mirrors from HW-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the front, clear glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×44 μm, with aweather barrier of an epoxy resin coupled with spacers of about 44 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 21(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 21(A), supra, wasuniformly applied within the mirror assemblies of Example 21(B), supra,we placed the assemblies onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assemblies to ultraviolet radiation inthe same manner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about -0.7 volts to one of the electrochromicmirrors of Examples 21(B) and (C), supra, and observed that mirrorreflectance at the center portion of the mirror remained high at about76%.

Upon reversing the polarity of the applied potential and increasing themagnitude to about +1.5 volts, we observed this mirror to color rapidlyand uniformly to a blue color.

In addition, we observed that the high reflectance at the center portionof the mirror decreased to a low reflectance of about 7.8%, with theresponse time for the reflectance to change from about 70% to about 20%when that potential was applied thereto being about 2.4 seconds. We madethis determination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 1.7 seconds under apotential of about -0.7 volts with a high reflectance of about 78%re-established. We noted that when a potential of about zero volts toabout -0.2 volts was applied to the mirror to bleach the mirror from thefully dimmed stated, the response time to achieve this effect was about2.0 seconds. We also noted that when a potential having a greatermagnitude, such as about -0.8 volts to about -0.9 volts, was applied tothe mirror, the color assumed by the polychromic solid film may becontrolled. For instance, a slight blue tint may be achieved at thataforestated greater negative potential using the electrochromic systemof this example so that the bleached state of the electrochromic mirrormay be matched to the color appearance of conventionalnon-electrochromic blue-tint mirrors commonly featured on luxuryautomobiles.

Example 22

In this example, we illustrate that a gradient opacity panel, such asthat which may be used as an electrochromic shade band on an automobilewindshield, may be created by configuring the bus bars on theelectrochromic assembly so they are affixed partially around, or alongthe opposite sides, of the assembly, thus creating a transition betweenthe areas of the device to which voltage is applied and those where novoltage is applied.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.1% EVClO₄ (as a cathodic compound), about 1.4% t-butyl ferrocene(as an anodic compound), both homogeneously dispersed in a combinationof about 54.2% propylene carbonate (as the plasticizer), and, incombination as a monomer component, about 28.6% B-565 and about 13.8%Urethane Acrylate (Soft) (CN 953). We thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Panel Assembly with Electrochromic Monomer Composition

We constructed a panel assembly containing an electrochromic shade bandby dispensing a portion of the electrochromic monomer composition ofExample 22(A), supra, onto the conductive surface of a HW-ITO coatedglass substrate having a sheet resistance of about 15 ohms per square.Onto this substrate we also placed 100 μm glass beads, and thenpositioned thereover another HW-ITO coated glass substrate having asheet resistance of about 15 ohms per square so that the electrochromicmonomer composition was between and in contact with the conductivesurface of the two glass substrates. The dimensions of the assembly wereabout 4.5"×14", with an interpane distance between the glass substratesof about 100 μm.

We connected bus bars along the 14" sides of the panel assembly onlyabout 4" inward from the edge of each of the opposing 14" sides. Wethereafter affixed electrical leads to the bus bars.

C. Transformation of Electrochromic Monomer Composition within PanelAssembly to Polychromic Solid Film

Once the electrochromic monomer composition of Example 22(A), supra, wasuniformly applied within the window panel assembly of Example 22(B),supra, we placed the assembly onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the panel assembly to ultravioletradiation in the same manner as described in Example 2(C), supra.

Once the polychromic solid film was formed, we applied a weather barrierof epoxy resin along, and over, the glass joints to prevent entry ofenvironmental contaminants. This weather barrier consisted of a bead of"ENVIBAR" UV 1244 ultraviolet curable adhesive followed by theapplication of "SMOOTH-ON" room temperature cure epoxy (commerciallyavailable from Smooth-On Inc., Gillette, N.J.).

D. Demonstration of Electrochromic Shade Band within Panel Assembly

We applied a potential of about 1.3 volts to the panel assembly, andthereafter observed that only the 4" region through which an electricfield was formed colored rapidly, uniformly and intensely to a bluecolor. We also observed that color extended beyond that 4" region for adistance of about 1" in a gradient opacity which changed gradually froman intense coloration immediately adjacent the bus bar/non-bus bartransition to a bleached appearance beyond that additional 1" region orthereabouts.

In addition, we observed that the high transmittance at the centerportion of the panel assembly was about 79.6% transmittance whichdecreased to a low transmittance of about 7.6%. The response time forthe transmittance to change from about 70% to about 20% was about 2.2seconds when a potential of about 1.5 volts was applied thereto. We madethat determination by the reflectometer described in Example 1, supra,except that the reflectometer was set in transmission mode.

We also observed that the panel assembly bleached from about 10%transmittance to about 60% transmittance in a response time of about 2.5seconds under about zero applied potential.

Example 23

In this example, like Example 3, supra, we installed the interiorautomotive mirror as a rearview mirror in an automobile to observe itsperformance under conditions attendant with actual use.

A. Preparation of Electrochiomic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.0% EVClO₄ (as a cathodic compound), about 1.3% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about62.6% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 8.9% caprolactone acrylate, about 13.4%polyethylene glycol diacrylate (400) and about 4.5% "SARBOX" acrylateresin (SB 500). We also added about 1.8% "IRGACURE" 184 (as aphotoinitiator) and about 4.5% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogenous dispersion of the components wasachieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled an interior automotive mirror with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×74 μm, with aweather barrier of an epoxy resin coupled with spacers of about 74 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 23(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 23(A), supra, wasuniformly applied within the mirror assembly of Example 23(B), supra, weplaced the assembly onto the conveyor belt of a Fusion UV Curing SystemF-300 B, and exposed the assembly to ultraviolet radiation in the samemanner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.0% reflectance which decreased to a lowreflectance of about 7.5%. The response time for the reflectance tochange from about 70% to about 20% was about 3.5 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 5.2 seconds underabout zero applied potential.

We have successfully installed and operated this mirror in an automobileas a rearview mirror and have achieved excellent results.

Example 24

In this example, we chose to illustrate the beneficial properties andcharacteristics of polychromic solid films manufactured within anelectrochromic sun roof panel.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 1.4% EVClO₄ (as a cathodic compound),about 0.9% t-butyl ferrocene (as an anodic compound), both homogeneouslydispersed in a combination comprising about 39% propylene carbonate (asa plasticizer), and, in combination as a monomer component, about 39%"QUICK CURE" B-565 and about 19.53% Urethane Acrylate (Soft) (CN 953).We thoroughly mixed this electrochromic monomer composition to ensurethat a homogeneous dispersion of the components was achieved.

B. Preparation of Sun Roof Panel Assembly and Placement ofElectrochromic Monomer Composition Therein

We prepared the glass substrates for use in the glazing assembly of thisexample by placing flat "TEC-20" glass substrates (with a black ceramicfrit band around their perimeter edge regions), having dimensions ofabout 12"×16", onto the mold of a bending instrument at room temperatureunder ambient conditions, and then increasing the temperature of thesubstrates to be bent to at least about 500° C. thereby causing thesubstrates to conform to the shape of the mold.

We also placed, as a spacer means, black drafting tape (Zipatone, Inc.,Hillsdale, Ill.), having a width of about 0.0625" and a thickness ofabout 150 μm, onto a conductive surface of one of the bent "TEC-20"glass substrates in about 1.5" intervals across the width of thesubstrate. At such intervals, we found the black drafting tape to bepositioned in an aesthetically appealing manner, and to maintainuniformity of the electrochromic media across the full dimensions of thepanel.

We assembled the sun roof panel by dispensing a portion of theelectrochromic monomer composition of Example 24(A), supra, onto theconductive surface of the substrate to be used as the concave interiorsurface (i.e., the Number 4 surface), and placed thereover theconductive surface of the substrate bearing the spacer means so that theelectrochromic monomer composition was between and in contact with theconductive surface of the glass substrates. We then placed the panelassembly in a vacuum bag, gently elevated the temperature and evacuatedsubstantially most of the air from the vacuum bag. In this way, theelectrochromic monomer composition dispersed uniformly between thesubstrates under the pressure from the atmosphere.

C. Transformation of Electrochromic Monomer Composition into PolychromicSolid Film

We then placed the sun roof panel assembly (still contained in thevacuum bag) into a Sunlighter model 1530 UV chamber, equipped with threemercury lamps (commercially available from Test-Lab Apparatus Co.,Milford, N.H.), and allowed the sun roof panel to remain exposed to theultraviolet radiation emitted by the lamps for a period of time of about30 minutes. The interpane distance between the "TEC-20" glass substrateswas about 150 μm.

We thereafter attached bus bars at the 12" side of the substrates tocreate a distance therebetween of about 16". We then attached electricalleads to the bus bars.

D. Use of Electrochromic Sun Roof Panel

We applied a potential of about 1.3 volts to the glazing assembly, andthereafter observed the panel to color rapidly and uniformly to a bluishpurple color.

In addition, we observed that the high transmission at the centerportion of the sun roof panel was about 67% transmission which decreasedto a low transmission of about 5% when about 1.3 volts was appliedthereto. The response time for the transmission to change from about 60%to about 10% when that potential was applied thereto was about 3minutes. We made this determination by the detection method described inExample 1, supra, except that the reflectometer was set in transmissionmode.

We also observed that the glazing assembly bleached from about 5%transmission to about 60% transmission in a response time of about 6.5minutes under about a zero applied potential.

The ultraviolet stability, scatter safety performance and/orelectrochromic performance, and reduction in transmittance ofnear-infrared radiation of sun roof panels manufactured in accordancewith the teaching herein, may be augmented by using the methods taughtin Lynam III and Lynam V, and in commonly assigned U.S. Pat. No.5,239,406 (Lynam)].

Example 25

In this example, we chose to illustrate the beneficial properties andcharacteristics of polychromic solid films manufactured within anelectrochromic sun visor having a segmented design.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition according to thepresent invention comprising about 2.4% EVClO₄ (as a cathodic compound),about 1.6% ferrocene (as an anodic compound), both homogeneouslydispersed in a combination comprising about 48% propylene carbonate (asa plasticizer), and, in combination as a monomer component, about 32%"QUICK CURE" B-565 and about 16% Urethane Acrylate (Soft) (CN 953). Wethoroughly mixed this electrochromic monomer composition to ensure thata homogeneous dispersion of the components was achieved.

B. Sun Visor with Electrochromic Monomer Composition

We assembled the sun visor of this example from FW-ITO coated glasssubstrates, having dimensions of about 4"×14" and a sheet resistance ofabout 6 to about 8 ohms per square, onto which we previously placeddeletion lines to form three individual segments. We created thesedeletion lines by screening a photo-resist material onto the glasssubstrate prior to depositing the ITO coating, and thereafter applying acoat of ITO onto the photo-resist coated substrate, and washing away thephotoetched resist material using an organic solvent, such as acetone.

We assembled the sun visor by placing onto the 14" edges of theconductive surface of one of the FW-ITO glass substrates "KAPTON" hightemperature polyamide tape (E. I. du Pont de Nemours and Company,Wilmington, Del.), having a thickness of 70 μm. We then dispensed aportion of the electrochromic monomer composition of Example 25(A),supra, onto that conductive surface and then placed thereover theconductive surface of another substrate so that the electrochromicmonomer composition was between and in contact with the conductivesurface of the glass substrates. The interpane distance between thesubstrates was about 70 μm.

C. Transformation of Electrochromic Monomer Composition within Sun Visorto Polychromic Solid Film

Once the electrochromic monomer composition of Example 25(A), supra, wasuniformly applied within the sun visor assembly of Example 25(B), supra,we placed the assembly onto the conveyor belt of a Fusion UV CuringSystem F-300 B, and exposed the assembly to ultraviolet radiation in thesame manner as described in Example 2(C), supra.

Upon completion of the transformation process, we applied "ENVIBAR" UV1244 to the glass edges and joints and again exposed the sun visor toultraviolet radiation to further weather barrier protect the sun visor.We then applied "SMOOTH-ON" epoxy to those portions of the sun visor toform a final weather barrier about the sun visor.

D. Use of Electrochromic Sun Visor

We applied a potential of about 1.3 volts to the sun visor, andthereafter observed the sun visor to color rapidly and uniformly to abluish purple color.

In addition, we observed that the high transmission at the centerportion of the sun visor was about 74.9% transmission which decreased toa low transmission of about 2.5% when about 1.5 volts was appliedthereto. The response time for the transmission to change from the hightransmission state to about 10% when that potential was applied theretowas about 9 seconds. We made this determination by the detection methoddescribed in Example 1, supra, except that the reflectometer was set intransmission mode.

We also observed that the sun visor bleached from about 10% transmissionto about 70% transmission in a response time of about 15 seconds underabout a zero applied potential.

The segmented portions of the sun visor of this example may be made in ahorizontal direction or a vertical direction, and individual segmentsmay be activated by connection to an individual segment addressingmeans, such as a mechanical switch, a photosensor, a touch sensor,including a touch activated glass panel, a voice activated sensor, an RFactivated sensor and the like. In addition, segments may be activatedindividually or as pluralities by responding to glare from the sun, suchas when the sun rises from and falls toward the horizon, or as ittraverses the horizon. This sun visor, as well as other electrochromicglazings, such as windows, sun roofs and the like, may use automaticglare sensing means that involve single or multiple photosensors, suchas those disclosed in U.S. Pat. No. 5,148,014 (Lynam).

Example 26

In this example, we assembled an interior automotive mirror as arearview mirror to be installed in an automobile to observe itsperformance under conditions attendant with actual use.

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.6% EVClO₄ (as a cathodic compound), about 1.6% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about61.9% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 11.1% polyethylene glycol monomethacrylate(400), about 11.1% polyethylene glycol diacrylate (400) and about 4.4%"SARBOX" acrylate resin (SB 500). We also added about 1.8% "IRGACURE"184 (as a photoinitiator) and about 4.4% "UVINUL" N 35 (as anultraviolet stabilizing agent), and thoroughly mixed this electrochromicmonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled an interior automotive mirror with HWG-ITO coated glasssubstrates (where the conductive surface of each glass substrate facedone another), with both the clear, front glass and the silvered, rearglass having a sheet resistance of about 15 ohms per square. Thedimensions of the mirror assemblies were about 2.5"×10"×53 μm, with aweather barrier of an epoxy resin coupled with spacers of about 53 μmalso applied.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 26(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 26(A), supra, wasuniformly applied within the mirror assembly of Example 26(B), supra, weplaced the assembly onto the conveyor belt of a Fusion UV Curing SystemF-300 B, and exposed the assembly to ultraviolet radiation in the samemanner as described in Example 1(D), supra.

D. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72.0% reflectance which decreased to a lowreflectance of about 7.4%. The response time for the reflectance tochange from about 70% to about 20% was about 2.1 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.0 seconds underabout zero applied potential.

Example 27

In this example, we assembled automotive mirrors for use with the 1993Lincoln Continental automobile. Specifically, Example 27(A), infra,illustrates the manufacture and use of an interior rearview mirror, andExample 27(B), infra, illustrates the use of an exterior mirror, sizedfor driver-side and passenger-side applications, to be installed in theautomobile.

A. 1993 Lincoln Continental Interior Rearview Mirror

1. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 3.6% EVClO₄ (as a cathodic compound), about 1.6% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about62% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 8.9% caprolactone acrylate, about 13.3%polyethylene glycol diacrylate (400) and about 4.4% "SARBOX" acrylateresin (SB 500). We also added about 1.8% "IRGACURE" 184 (as aphotoinitiator) and about 4.4% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

2. Interior Rearview Mirror Assembly with Electrochromic MonomerComposition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 27(A)(1), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

3. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 27(A)(1), supra,was uniformly applied within the mirror assembly of Example 27(A)(2),supra, we placed the assembly onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assembly to ultraviolet radiationin the same manner as described in Example 1(D), supra.

4. Use of Electrochromic Mirror

We applied a potential of about 1.5 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 76.5% reflectance which decreased to a lowreflectance of about 7.4%. The response time for the reflectance tochange from about 70% to about 20% was about 2.2 seconds when apotential of about 1.5 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 2.7 seconds underabout zero applied potential.

B. 1993 Lincoln Continental Exterior Mirrors--Driver-Side andPassenger-Side

1. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 2.6% EVClO₄ (as a cathodic compound), about 1.2% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about63% propylene carbonate (as a plasticizer), and, in combination as amonomer component, about 9% caprolactone acrylate, about 13.5%polyethylene glycol diacrylate (400) and about 4.5% "SARBOX" acrylateresin (SB 500). We also added about 1.8% "IRGACURE" 184 (as aphotoinitiator) and about 4.5% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

2. Exterior Mirror Assemblies with Electrochromic Monomer Composition

We assembled exterior mirrors, with an interpane distance of 74 μm, fromFW-ITO coated 063 glass substrates (where the conductive surface of eachglass substrate faced one another), with both the clear, front glass andthe silvered, rear glass having a sheet resistance of about 6 to about 8ohms per square. We also applied a weather barrier of an epoxy resincoupled with spacers of about 74 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 27(B)(1), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

3. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 27(B)(1), supra,was uniformly applied within the mirror assemblies of Example 27(B)(2),supra, we placed the assemblies onto the conveyor belt of a Fusion UVCuring System F-300 B, and exposed the assemblies to ultravioletradiation in the same manner as described in Example 1(D), supra.

4. Use of Electrochromic Mirrors

We applied a potential of about 1.5 volts to one of the mirrors, andthereafter observed rapid and uniform coloration to a blue color with agreenish hue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 72% reflectance which decreased to a lowreflectance of about 8%. The response time for the reflectance to changefrom about 70% to about 20% was about 3.9 seconds when a potential ofabout 1.5 volts was applied thereto. We made that determination by thereflectometer described in Example 1, supra.

We also observed that the mirror bleached from about 10% reflectance toabout 60% reflectance in a response time of about 4.0 seconds underabout zero applied potential.

Example 28

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 6.31% HVSS (as a cathodic compound), about 1.63% ferrocene (as ananodic compound), both homogeneously dispersed in a combination of about47.48% propylene carbonate and about 8.63% 3-hydroxypropionitrile (as aplasticizer), and, in combination as a monomer component, about 12.95%caprolactone acrylate, about 8.63% polyethylene glycol diacrylate (400)and about 8.63% "SARBOX" acrylate resin (SB 501). We also added, incombination as photoinitiators, about 0.13% "IRGACURE" 184 and about1.29% "CYRACURE" UVI-6990 and about 4.32% "UVINUL" N 35 (as anultraviolet stabilizing agent), and thoroughly mixed this electrochromicmonomer composition to ensure that a homogeneous dispersion of thecomponents was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 28(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 28(A), supra, wasuniformly applied within the mirror assembly of Example 28(B), supra, weplaced the assembly onto the conveyor belt of a Hanovia UV Curing System(Hanovia Corp., Newark, N.J.), fitted with UV lamp 6506A431, with theintensity dial set at 300 watts. We exposed the assembly to ultravioletradiation in a similar manner as described in Example 1(D), supra, bypassing the assembly under the UV lamp with the conveyor speed set atabout 20% to about 50% for about 120 to about 180 multiple passes.

D. Use of Electrochromic Mirror

We applied a potential of about 1.2 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 73.9% reflectance which decreased to a lowreflectance of about 7.4%. The response time for the reflectance tochange from about 70% to about 20% was about 3.9 seconds when apotential of about 1.2 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

Example 29

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.38% DSMVClO₄ (as a cathodic compound) and about 0.57% EHPVClO₄(as a cathodic compound), about 1.62% ferrocene (as an anodic compound),both homogeneously dispersed in a combination of about 56.74% propylenecarbonate (as a plasticizer), and, in combination as a monomercomponent, about 13.10% caprolactone acrylate, about 8.73% polyethyleneglycol diacrylate (400), about 4.37% "SARBOX" acrylate resin (SB 500E50)and about 4.37% "CYRACURE" resin UVR-6110. We also added, in combinationas photoinitiators, about 0.44% "IRGACURE" 184 and about 1.31%"CYRACURE" UVI-6990 and about 4.37% "UVINUL" N 35 (as an ultravioletstabilizing agent), and thoroughly mixed this electrochromic monomercomposition to ensure that a homogeneous dispersion of the componentswas achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 29(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 29(A), supra, wasuniformly applied within the mirror assembly of Example 29(B), supra, weplaced the assembly onto the conveyor belt of a Hanovia UV Curing System(Hanovia Corp., Newark, N.J., fitted with UV lamp 6506A431, with theintensity dial set at 300 watts. We exposed the assembly to ultravioletradiation in a similar manner as described in Example 1(D), supra, bypassing the assembly under the UV lamp with the conveyor speed set atabout 20% to about 50% for about 120 to about 180 multiple passes.

D. Use of Electrochromic Mirror

We applied a potential of about 1.2 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 79.6% reflectance which decreased to a lowreflectance of about 6.7%. The response time for the reflectance tochange from about 70% to about 20% was about 2.8 seconds when apotential of about 1.2 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

Example 30

A. Preparation of Electrochromic Monomer Composition

We prepared an electrochromic monomer composition comprising by weightabout 4.42% DSMVClO₄ (as a cathodic compound) and about 0.59% EHPVClO₄(as a cathodic compound), about 1.65% ferrocene (as an anodic compound),both homogeneously dispersed in a combination of about 48.67% propylenecarbonate (as a plasticizer), and, in combination as a monomercomponent, about 13.27% caprolactone acrylate, about 8.85% polyethyleneglycol diacrylate (400), about 8.85% "SARBOX" acrylate resin (SB 500E50)and about 8.85% "CYRACURE" resin UVR-6110. We also added, in combinationas photoinitiators, about 0.44% "IRGACURE" 184 and about 1.77%"CYRACURE" UVI-6990 and about 2.65% 2-hydroxy-4-octoxybenzophenone (asan ultraviolet stabilizing agent), and thoroughly mixed thiselectrochromic monomer composition to ensure that a homogeneousdispersion of the components was achieved.

B. Mirror Assembly with Electrochromic Monomer Composition

We assembled an interior rearview mirror, with an interpane distance of53 μm, from HWG-ITO coated 093 glass substrates (where the conductivesurface of each glass substrate faced one another), with both the clear,front glass and the silvered, rear glass having a sheet resistance ofabout 15 ohms per square. We also applied a weather barrier of an epoxyresin coupled with spacers of about 53 μm.

We placed into these mirror assemblies the electrochromic monomercomposition of Example 30(A), supra, using the vacuum backfillingtechnique [as described in Varaprasad III, supra].

C. Transformation of Electrochromic Monomer Composition within Mirror toPolychromic Solid Film

Once the electrochromic monomer composition of Example 30(A), supra, wasuniformly applied within the mirror assembly of Example 30(B), supra, weplaced the assembly onto the conveyor belt of a Hanovia UV Curing System(Hanovia Corp., Newark, N.J., fitted with UV lamp 6506A431, with theintensity dial set at 300 watts. We exposed the assembly to ultravioletradiation in a similar manner as described in Example 1(D), supra, bypassing the assembly under the UV lamp with the conveyor speed set atabout 20% to about 50% for about 120 to about 180 multiple passes.

D. Use of Electrochromic Mirror

We applied a potential of about 1.3 volts to the mirror, and thereafterobserved rapid and uniform coloration to a blue color with a greenishhue.

In addition, we observed that the high reflectance at the center portionof the mirror was about 71.9% reflectance which decreased to a lowreflectance of about 6.9%. The response time for the reflectance tochange from about 70% to about 20% was about 3.9 seconds when apotential of about 1.3 volts was applied thereto. We made thatdetermination by the reflectometer described in Example 1, supra.

While we have provided the above examples of the foregoing invention forillustrative purposes employing preferred electrochromic compounds,monomer components and plasticizers, and other components it is to beunderstood that variations and equivalents of each of the preparedelectrochromic monomer compositions identified herein will providesuitable, if not comparable, results when viewed in connection with theresults gleaned from these examples. Without undue experimentation,those of ordinary skill in the art will find it readily apparent toprepare polychromic solid film with the beneficial properties andcharacteristics desirable for the specific application armed with theteaching herein disclosed. And, it is intended that such equivalents beencompassed by the claims which follow hereinafter.

What we claim is:
 1. An electrochromic window device suitable for use ina vehicle or building comprising:(a) a first transparent rigid substratehaving a transparent conductive layer on a surface thereof; (b) a secondtransparent rigid substrate having a transparent conductive layer on asurface thereof, said conductive layer of said first substrate opposingsaid second conductive layer of said second substrate in a spaced-apartrelationship thereby forming an interpane distance between saidsubstrates; (c) a boundary seal interposed between said first and secondsubstrates spacing apart said substrates and forming a cavity whereinsaid interpane distance is at least about 10 μm and wherein saidboundary seal forms a weather barrier for said cavity; (d) anelectrochromic cross-linked polymeric solid film within said cavity,said electrochromic cross-linked solid polymeric film formed by curingwithin said cavity an electrochromic monomer composition that includesat least one of (A) a monofunctional monomer and a cross-linking agentand (B) a polyfunctional monomer capable of cross-linking, and furtherincluding (i) at least one anodic electrochromic compound; (ii) at leastone cathodic electrochromic compound; (iii) a plasticizer; and (e) ameans for introducing an applied potential to said electrochromiccross-linked polymeric solid film to controllably cause a variation inthe amount of light transmitted through said device.
 2. Anelectrochromic window device suitable for use in a vehicle or buildingcomprising:(a) a first transparent rigid substrate having a transparentconductive layer on a surface thereof, said conductive layer of saidfirst substrate having a break in electrical continuity; (b) a secondtransparent rigid substrate having a transparent conductive layer on asurface thereof, said conductive layer of said first substrate opposingsaid conductive layer of said second substrate in a spaced-apartrelationship thereby forming an interpane distance between saidconductive layers of said substrates, and said conductive layer ofsecond substrate having a break in electrical continuity in linearalignment with that of the break in electrical continuity of theconductive layer of said first substrate; (c) a boundary seal interposedbetween said first and second substrates spacing apart said substratesand forming a cavity wherein said interpane distance is at least about10 μm and wherein said boundary seal forms a weather barrier for saidcavity; (d) an electrochromic cross-linked polymeric solid film withinsaid cavity, said electrochromic cross-linked polymeric solid filmformed by curing within said cavity an electrochromic monomercomposition that includes at least one of (A) a monofunctional monomerand a cross-linking agent and (B) a polyfunctional monomer capable ofcross-linking, and further including (i) at least one anodicelectrochromic compound; (ii) at least one cathodic electrochromiccompound; (iii) a plasticizer; and (e) a means for introducing anapplied potential to a pre-determined portion of said electrochromiccross-linked polymeric solid film which controllably causes a variationin the amount of light transmitted through a pre-determined portion ofsaid device.
 3. The electrochromic device according to claim 1 or 2,wherein the conductive layer of said first transparent substrate and theconductive layer of said second transparent substrate may beindependently selected from a material selected from the groupconsisting of indium tin oxide, indium tin oxide full wave, indium tinoxide half wave, indium tin oxide half wave green, tin oxide,antimony-doped tin oxide, fluorine-doped tin oxide, antimony-doped zincoxide and aluminum-doped zinc oxide.
 4. The electrochromic deviceaccording to claim 1 or 2, wherein said device is a member selected fromthe group consisting of a vehicular window, vehicular windshield,vehicular backlight, vehicular sun roof, vehicular sun visor, vehicularshade band, building window, building partition or sky light.
 5. Theelectrochromic device according to claim 1 or 2, further comprising amolded casing formed about the periphery of the device.
 6. Theelectrochromic device according to claim 5, wherein said molded casingis selected from constructions of injection molded polyvinyl chlorideand a material formed by reaction injection molding.
 7. Theelectrochromic device according to claim 1 or 2, wherein at least one ofsaid substrates is constructed from tinted glass.
 8. The electrochromicdevice according to claim 1 or 2, wherein said interpane distance isfrom about 10 μm to about 1000 μm.
 9. The electrochromic deviceaccording to claim 8, wherein said interpane distance is from about 20μm to about 200 μm.
 10. The electrochromic device according to claim 9,wherein said interpane distance is from about 37 μm to about 74 μm. 11.The electrochromic device according to claims 1 or 2, wherein saidboundary seal is made from a polymeric material.
 12. The electrochromicdevice according to claims 11, wherein said polymeric material comprisesan epoxy resin, a plasticized polyvinyl butyral, an ionomer resin, apolyamide material, a nitrile containing polymer, or a butyl rubber. 13.The electrochromic device according to claims 11, wherein said boundaryseal comprises spacers.
 14. The electrochromic device according to claim1 or 2, wherein said electrochromic monomer composition includes amonomer component selected from the group consisting of acrylatedurethanes, acrylated heterocyclics and acrylate resins.
 15. Theelectrochromic device according to claim 1 or 2, wherein saidelectrochromic monomer composition further comprises a componentselected from the group consisting of photoinitiators, photosensitizers,ultraviolet stabilizing agents, electrolytic materials, coloring agents,spacers, anti-oxidizing agents, flame retarding agents, heat stabilizingagents, compatibilizing agents, humectants, lubricating agents, adhesionpromoting agents, coupling agents and combinations thereof.
 16. Theelectrochromic device according to claim 1 or 2, wherein saidelectrochromic monomer composition comprises a cross-linking agent. 17.The electrochromic device according to claim 16, wherein saidcross-linking agent is selected from the group consisting ofpolyfunctional hydroxy compounds, polyfunctional primary or secondaryamino compounds, polyfunctional mercapto compounds and combinationsthereof.
 18. The electrochromic device according to claim 17, whereinsaid cross-linking agent comprises a polyfunctional hydroxy compound.19. The electrochromic device according to claim 18, wherein saidpolyfunctional hydroxy compound comprises a polyol.
 20. Theelectrochromic device according to claim 19, wherein said polyolcomprises a glycol or a glycerol.
 21. The electrochromic deviceaccording to claim 16, wherein said cross-linking agent is selected fromthe group consisting of pentaerythritol,2-ethyl-2-(hydroxymethyl)-1,3-propanediol, caprolactone triols, andcombinations thereof.
 22. The electrochromic device according to claim 1or 2, wherein said monomer composition comprises a monomer componentwhich polymerizes by addition polymerization or ring openingpolymerization selected from the group consisting of a monofunctionalmonomer, a difunctional monomer, a trifunctional monomer, apolyfunctional monomer or mixtures thereof.
 23. The electrochromicdevice according to claim 22, wherein said monomer component is selectedfrom the group of monomers consisting of 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, methylene glycol monoacrylate, diethyleneglycol monomethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropylmethacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate,dipropylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate,methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate,n-butyl acrylate, s-butyl acrylate, n-pentyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, ethyl methacrylate, n-propylmethacrylate, i-propyl methacrylate, n-butyl methacrylate, s-butylmethacrylate, n-pentyl methacrylate, s-pentyl methacrylate, methoxyethylacrylate, methoxyethyl methacrylate, triethylene glycol monoacrylate,glycerol monoacrylate, glycerol monomethacrylate, benzyl acrylate,caprolactone acrylate, cyclohexyl acrylate, cyclohexyl methacrylate,2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate,2-(2-ethoxyethoxy)-ethylacrylate, glycidyl methacrylate, n-hexylacrylate, n-hexyl methacrylate, isobornyl acrylate, isobornylmethacrylate, i-decyl acrylate, i-decyl methacrylate, i-octyl acrylate,lauryl acrylate, lauryl methacrylate, 2-methoxyethyl acrylate, n-octylacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, stearylacrylate, stearyl methacrylate, tetrahydrofurfuryl acrylate,tetrahydrofurfuryl methacrylate, tridecyl methacrylate, 1,4-butanedioldiacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycoldiacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycoldiacrylate, diethylene glycol dimethacrylate, ethylene glycoldiacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycoldimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, polyethylene glycol diacrylate, polyethylene glycoldimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, triethylene glycol diacrylate, triethylene glycoldimethacrylate, tripropylene glycol diacrylate, dipentaerythritolpentaacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritoltetraacrylate, trimethylolpropane triacrylate, pentaerythritoltriacrylate, trimethylolpropane trimethacrylate,tris(2-hydroxyethyl)-isocyanurate triacrylate,tris(2-hydroxyethyl)-isocyanurate trimethacrylate, polyethylene glycolmonoacrylate, polyethylene glycol monomethacrylate, polypropylene glycolmonoacrylate, polypropylene glycol monomethacrylate, hydroxyethylcellulose acrylate, hydroxyethyl cellulose methacrylate, methoxypoly(ethyleneoxy) ethylacrylate, methoxy poly(ethyleneoxy)ethylmethacrylate, ethylene glycol diacrylate, ethylene glycoldimethacrylate, 1,2-butylene dimethacrylate, 1,3-butylenedimethacrylate, 1,4-butylene dimethacrylate, propylene glycoldiacrylate, propylene glycol dimethacrylate, dipropylene glycoldiacrylate, divinyl benzene, divinyl toluene, diallyl tartrate, allylmaleate, divinyl tartrate, triallyl melamine, glycerine trimethacrylate,diallyl maleate, divinyl ether, diallyl monomethylene glycol citrate,ethylene glycol vinyl allyl citrate, allyl vinyl maleate, diallylitaconate, ethylene glycol diester of itaconic acid, polyester of maleicanhydride with triethylene glycol, polyallyl glucoses, polyallylsucroses, glucose dimethacrylate, pentaerythritol tetraacrylate,sorbitol dimethacrylate, diallyl aconitate, divinyl citrasonate, diallylfumarate, allyl methacrylate,1,3-bis-(4-benzoyl-3-hydroxyphenoxy)-2-propylacrylate,2-hydroxy-4-acryloxyethoxybenzophenone,4-methacryloxy-2-hydroxybenzophenone, cyclohexene oxide, cyclopenteneoxide, glycidyl i-propyl ether, glycidyl acrylate, furfuryl glycidylether, styrene oxide, ethyl-3-phenyl glycidate, 1,4-butanediol glycidylether, 2,3-epoxypropyl-4-(2,3-epoxypropoxy) benzoate,4,4'-bis-(2,3-epoxypropoxy)biphenyl and combinations thereof.
 24. Theelectrochromic device according to claim 1 or 2, wherein saidplasticizer is selected from the group consisting of acetonitrile,benzylacetone, 3-hydroxypropionitrile, methoxypropionitrile,3-ethoxypropionitrile, propylene carbonate, ethylene carbonate,glycerine carbonate, 2-acetylbutyrolactone, cyanoethyl sucrose,7-butyrolactone, 2-methylglutaronitrile, N,N'-dimethylformamide,3-methylsulfolane, methylethyl ketone, cyclopentanone, cyclohexanone,4-hydroxy-4-methyl-2-pentanone, acetophenone, glutaronitrile,3,3'-oxydipropionitrile, 2-methoxyethyl ether, triethylene glycoldimethyl ether and combinations thereof.
 25. The electrochromic deviceaccording to claim 1 or 2, wherein said cathodic electrochromic compoundcomprises a viologen or an anthraquinone.
 26. The electrochromic deviceaccording to claim 22, wherein said cathodic electrochromic compound maybe selected from the group consisting of ethylviologen perchlorate,heptylviologen styryl sulfonate, distyrylmethylviologen perchlorate,ethylhydroxypropylviologen perchlorate and combinations thereof.
 27. Theelectrochromic device according to claim 1 or 2, wherein said anodicelectrochromic compound is selected from the group consisting ofphenothiazines, phenazines, metallocenes and combinations thereof. 28.The electrochromic device according to claim 27, wherein said anodicelectrochromic compound is selected from the group consisting of2-methyl-phenothiazine-3-one having been previously contacted with aredox agent, 5,10-dihydro-5,10-dimethylphenazine, ferrocene andcombinations thereof.
 29. The electrochromic device according to claim 1or 2, wherein said electrochromic cross-linked polymeric solid filmcomprises a cross-linked urethane, a cross-linked epoxy, a cross-linkedacrylate, a cross-linked vinyl or a combination thereof.